explicitlym.kan84.net

EntangledTwo-DimensionalCoordinationNetworks:AGeneralSurveyLuciaCarlucci,*,GianfrancoCiani,DavideM.
Proserpio,*,,TatianaG.
Mitina,andVladislavA.
Blatov*,,§DipartimentodiChimica,UniversitadegliStudidiMilano,ViaC.
Golgi19,20133Milano,ItalySamaraCenterforTheoreticalMaterialsScience,SamaraStateUniversity,Ac.
PavlovStreet1,Samara443011,Russia§ChemistryDepartment,FacultyofScience,KingAbdulazizUniversity,PostOceBox80203,Jeddah21589,SaudiArabia*SSupportingInformationCONTENTS1.
Introduction75572.
AnalysisofCrystalStructuresbyTOPOS75583.
TopologiesandEntanglementsofTwo-Dimen-sionalCoordinationMotifs75593.
1.
Interpenetration75603.
2.
EntanglementsofTwo-DimensionalLayersContaining2-MemberedLoops75633.
3.
ParallelPolycatenation75653.
4.
InclinedPolycatenation75673.
5.
BorromeanLinks75703.
6.
MixedTypesofEntanglementof2DMotifs75734.
Conclusions7576AssociatedContent7576SupportingInformation7576AuthorInformation7576CorrespondingAuthors7576Notes7576Biographies7577Acknowledgments7578References75781.
INTRODUCTIONManycurrentinvestigationsarefocusedonthedesignofnewmolecule-basedfunctionalmaterials.
Agreatvarietyofextendedarchitectureswithpromisingpropertieshasbeenobtainedonthebasisofcrystalengineeringconcepts,bothmetalorganicandinorganicnetworkssupportedbycoordinative/valencebondsandsupramoleculararraysoforganicandmetalorganicmoleculessustainedbyhydrogenbondsorotherweakinteractions.
1Manyofthereportedspeciesexhibittheintriguingfeatureofinterpenetrationorothertypesofentanglements.
Thepropertiesofthesematerialsarerelatednotonlytotheirmolecularstructuresbutalsotothetopologyoftheindividualnetworksaswellastothewayinwhichtheindividualnetsareentangled.
Itisthereforeofbasicrelevancetoanalyzeandclassifytheseentanglements;inthisconcern,manycontributionshaveappearedinrecentyears,dealingwithrationalizationofnetinterpenetrationandelucidationofthedierenttypesofentangledsystems.
2Theextendedspeciesbasedontwo-dimensional(2D)polymericmotifs(seeFigure1fortheevolutionofreported2Dstructuresovertheyears)showparticularlyintriguingstructuresformanyreasons:theyexhibitalargevarietyofdistincttopologiesofsingle2Dnetsand,inaddition,showmanydierententanglementtypes,amongwhichsomepuzzlingcaseswerefoundthatneedadetaileddiscussion.
3WemustmentionheretheverycomplicatedandintriguingcaseoftheH-bondednetworkoftrimesicacid,consistingofunusuallypolycatenatedhoneycomb(hcb)2Dlayers,reportedmanyyearsago(1969).
4Wehavealreadyreportedourstudies,basedontheuseofTOPOS(apackageformultipurposecrystallochemicalanal-ysis),7oninterpenetrationinvalence-bondedcoordination2dandinorganicnetworks,8aswellasinhydrogen-bondedsupra-molecularthree-dimensional(3D)arraysformedbyorganicmolecules9orbymolecularcomplexes(zero-dimensional,0D)andone-andtwo-dimensional(1Dand2D)coordinationpolymers.
10Wereportherethecomprehensiveresultsofouranalysisofentanglementsincoordination2DnetworksfromtheCam-bridgeStructuralDatabase(CSD,version5.
34,November2012)usingthelatestversionofTOPOS.
Onlyvalence-bonded2Dmetal-basedcoordinationnetworksareconsideredhere,thatcanproducedierenttypesofentangledsystems;supramolecularframeworksobtainedbyhydrogenbondsand/orotherweakinteractionslikehalogenbondswillbeconsideredinfuturework.
Accordingtoourpreviousinvestigations,2c,e,fwehaveobservedthatthesedierenttypescanbeclassiedasinterpenetrated,polycatenated(parallelorinclined),orBorromean-linkedarrays.
Indeed,othersubclasseshavebeenevidencedandwillbediscussedbelow.
Received:March14,2014Published:June11,2014Reviewpubs.
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2014,114,75577580TermsofUseAfterthisclassication,wehavealsoexaminedthepotentialfunctionalapplicationsoftheseentangledspeciesinordertopossiblyestablishastructure/propertiesrelationshipdependingonthetypeofentanglement.
Porosityhasbeenoneoftherstrecognizedandinvestigatedpropertiesofcoordinationnetworks,andthesearchforrobustandsecond-generationporouscoordinationnetworkshasbeenstronglypursued,openingperspectivesforrealapplicationofthesecrystallinematerialsinmanytechnologicalelds.
Easytailoringofporesizeandshape,aswellaseasychemicalfunctionalizationofthenetworkedstructures,introducefeaturesnotcharacterizedbeforeforotherporousmaterials.
Flexibility/dynamismisoneofthesefeaturesandthemainoriginfornetworksoftness,atopicofincreasinginterest,addressedintheliteraturebymanyreviewsandarticles.
11Itisassociatedwiththeoccurrenceofareversiblestructuralchangeasaconsequenceofchemicalorphysicalexternalstimulisuchasinteractionwithguestmolecules,pressure,temperature,light,andsoon.
Thisstructuralexibilitycanbeadvantageouslyusedtodevelopporoussoftmaterialswithincreasedguestselectivitytobeused,forexample,assensorsoringasseparationtechnologies.
Entanglementcanbeexploitedtodeveloptailoredexiblematerials.
Reducingtheaccessiblefreespaceofaporousnetworkwasnegativelyconsideredforalongtime,butrecentlyithasregainedalotofinterest.
Infact,itcanbeusedtoincreasenetworkstabilityandtotailortheshapeandsizeofpores,increasingguestadsorptionselectivity;andmoreover,themutualdisplacementofentangledrigidorexiblemotifsisoneofthemechanismsattheoriginofsoftnessincoordinationnetworks.
Inaddition,interpenetrationcanaectthephysicalpropertiesofthematerial,forexample,magnetism.
12Dierentsyntheticprocedureshavebeendevelopedtoattainacertaincontrolofentanglementincoordinationnetworks,andrecentlysomereviewshaveappearedthatarefocusedonfactorsgoverningtheentanglements,havinginmindtheirpotentialapplications;13however,theseanalysesaremostlydevotedto3Dnetworksthankstothegreatwealthofdataoninter-penetration.
2dOntheotherhand,informationonentanglementsin2Dspecies,showingaremarkablerichnessoftypes,isstillmuchscatteredintheliterature(withthepropertiesonlyoccasionallyinvestigated),andageneralsurveyandration-alizationofthephenomenaistimely.
2.
ANALYSISOFCRYSTALSTRUCTURESBYTOPOSAllproceduresonsearch,retrieval,andtopologicalanalysisofthecrystalstructuresaswellastheirrepresentationwereperformedwiththeprogrampackageTOPOS.
7Thefollowinggeneralalgorithmwasused,allstepsofwhichareimplementedasTOPOSprocedures.
Thesesteps(IVI)aredescribedhereinfulldetail,whiletheresultsarediscussedstartinginsection3.
(I)Interatomicbondsweredeterminedbythemethodofintersectingsectorsthatweappliedrecentlyfor3Dcoordinationnetworks.
2d,14ThismethodusesVoronoipolyhedrainadditiontoatomicradiitodeterminevalencebonds;itisbestsuitedfororganicandcoordinationcompounds.
Weconsideredonlycoordinationcompounds;bondswithparticipationofalkalioralkaline-earthmetals(Na,K,Rb,Cs,Ca,Sr,andBa),aswellasallmetalmetalbonds,wereignored.
(II)Forallcoordinationnetworks,wedeterminedtheirperiodicity.
ThefollowingTOPOSalgorithmwasapplied:startingfromanymetalatomAofthenetwork,allthosetranslationallyequivalentATatomsaresearchedthatareconnectedtoAbychainsofbondsA-(L-A′-L)-ATofanylength(whereLisaniteligandofanycomplexityandA′isanatomrelatedtoAbyanontranslationalsymmetryoperation).
Thenumberofindependenttranslations(0,1,2,or3)thatrelateAandATatomsdeterminesthenetworkperiodicity.
Atthenextsteps,wehavetreatedonly2-periodicnetworks.
Inthisreview,weprefertotalkof2Dnetas2-periodic,withthedistinctionof2-periodic2Dnetsfortheonesthathaveaprojectiononaplanewithoutcrossingedgesand/orcoincidentvertices,hencetopologicallyplanarnets,andthicklayersforthe2-periodic3Dnetsthatinsteadcannotbeprojectedonaplanewithoutcrossingedgesand/orcoincidentvertices.
(III)All2Dnetworksweretestedfortheexistenceofentanglements.
WeassumedthatthetopologicalentanglementexistedifatleastoneHopflinkoramultilinkoccurredbetweendierent2Dmotifs.
Separately,wesearchedforBorromeanandBrunnianentanglementsinwhichonlynon-HopfinterweavingexistedwithineachgroupofNnetworksbutallNnetworksFigure1.
(Left)Distributionof2Dentangledcoordinationnetworkssince1994.
Therstexamplewasreportedin1966(notshown)withsilvertricyanomethide,AgC(CN)3[AGMANI],givinga2-foldinterpenetratedhcbnetwork,correctlydescribedbyKonnertandBritton.
5(Right)Distributionofsingle(notentangled)2Dcoordinationnetworkssince1994(dataupto2011weretakenfromref3).
Thetrendsfollowtheexplosionofinterestofresearchintotherealmofcoordinationnetworksandmetalorganicframeworks(MOFs).
6Notefromthegraphsthatnonentangledspeciesareabout8timesmorefrequentthanentangledones.
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2014,114,755775807558formedatightenedinterlacingarray,withN=3for2DBorromeanandN>3forboth2Dand3DBorromeanorBrunniantypesofentanglement.
Allentangledarraysfoundwerefurtheranalyzedatthenextsteps.
(IV)Thefollowingparametersofentanglementweredetermined:(a)entanglementtype(interpenetration,inclinedorparallelpolycatenation,BorromeanorBrunnianentangle-ment);(b)numberofentanglednetsintheinterpenetratedarray(Z);(c)degreeofcatenation(Doc)2cforinclinedorparallelpolycatenation,implyingevaluationofthenumberoflinks(Hopformultilink)aparticularringofonenetformswithringsofothernetsinthearray;(d)indexofseparation(Is)2cof2Dmotifsinthecaseofparallelpolycatenation,thatis,thenumberofmotifswhichhavetoberemovedtodisjointhearrayintotwoseparateparts;and(e)existenceof2-loops,thatis,ringsinwhichallnodes,buttwo,havecoordination2.
(V)Allthenetworkswerethensimpliedtoobtaintheunderlyingnets,thatis,netsofcentroidsofstructuralgroups.
Wehavetreatedtwotypesofsimplication:theclusterone,wheresomestructuralgroupswerepolynuclearcomplexes,andthestandardone,whereallmetalatomsandligandswereregardedasnodesoftheunderlyingnet.
Iftheunderlyingnetcontained1-or2-coordinatednodes(terminalorbridgestructuralgroups),itwassimpliedfurtherbyremovingtheterminalnodesandreplacingthebridgenodesbynetedges.
Simplicationofanetworkthatcontains2-loopscanleadtocompletedisappear-anceoftheentanglement,andthereforesuchnetworkswerepickedoutintoaseparategroup.
14Wedecidedtoreportonlyonetypeofunderlyingnetforeachstructure;inparticular,aclusterdescriptionwasusedwhenstructuralbuildingunitswereevident(e.
g.
,paddlewheels,dimers,etc.
)15(VI)TheoveralltopologiesofunderlyingnetsweredeterminedwiththeTOPOSTTDcollection,whichcurrentlycontainsmorethan75000nettopologies.
Todesignatethetopologieswehaveusedthreenomenclatures:ReticularChemistryStructureResource(RCSR)three-lettersymbols,16whichwereintroducedforthesimplestplanenets;FischerandKoch'ssymbolsfor2Dpackingofspheres;17andTOPOSNDksymbols,14whichareusedintheTOPOSTTDcollectionforthosetopologiesthatarenotcoveredbythersttwonomenclatures.
3.
TOPOLOGIESANDENTANGLEMENTSOFTWO-DIMENSIONALCOORDINATIONMOTIFSTheresultsofourinvestigationhaverevealedthatthereare7832Dmotifsthatformentangledarrays,representingca.
7%ofthetotalnumberofthestructurallycharacterized2Dspecies.
3Wehave,atrst,analyzedthetopologiesofindividual2Dmotifsformingtheentangledarraysandwefound36distinctnets(allillustratedinFigures3,4,and11andFigureS1inSupportingInformation).
Thedistributionofnetworktopologiesappearingatleasttwotimes(13outofthe36distincttopologiesoverallobserved)isillustratedinFigure2.
Amongthe36dierentnetworktopologiesfoundwithinall783analyzedstructures,sqlisthemostcommon,with465cases,andhcbissecond,with206cases.
Theremaining112structuresshow34dierenttop-ologies,and23ofthesearerepresentedbyasinglestructure.
Nineofthe36characterizedtopologiesareintrinsicallyplanar2-periodic2D(theirprojectiondoesnothaveanyedgecrossings)andaccountfor90%ofallstructures(706/783)(Figure3);allninetopologieshavebeenobservedalsonotentangled.
3The27remainingtopologiesarethicklayersormultilayers(2-periodic3D)andreferto77structures,65ofwhichareparallelpolycatenated(PCAT)with20dierenttopologies,eightinterpenetrated(INT),oneinclinedpolycatenated(ICAT),andthreewithmixedtypesofentanglement.
Thedierenttypesofentanglementdescribedherewereintroducedsomeyearsago;2c,e,ftheyarediscussedindetailbelow.
Acomparisonofsingle3versusentangled2Dnetsshowsthatsqlandhcbarethemostfrequentinbothcases;moreover,10entanglednetsamongtherst11observed(>2)(listedinFigure2)arealsofoundamongtherst14mostfrequentsingle2Dnets.
Tenthick-layernets,including3,3,4,4L30(eightoccurrences)andnineothertopologies(withoneoccurrenceeach),areobservedexclusivelywithinentangledspecies(seeFigures4and11).
Theremaining17thicklayers,observedalsoinnon-entangledspecies,arereportedinFigureS1inSupportingInformation.
Withinthethicklayersthe3-c(82.
10)-KIanet(seeFigure5)ispeculiarsinceitshowstheuncommonphenomenonofdierentrealizationofthesamegraphinspace(embeddings)thatcannotbedeformedintoeachotherwithoutbreakingedges;thispropertyiscalled"non-ambientisotopy".
2e,hWeobservedhereandalsointheanalysisofnonentangledcases(indetail:sevenPCAT,twoINT,and69nonentangledstructures)threedierentnonambientisotopicembeddingsof(82.
10)-KIanet,asillustratedinFigure5.
AllthestatisticsillustratedabovecanbecheckedindetailwiththedataavailableasSupportingInformationTwoplanarnetsthatrankinthetop10listofmostfrequentsingle2Dlayersdonotgiveentanglement:36-hxl(hexagonallattice),likelyduetothepresenceofthesmallest3-ringsand4,4L1,whicharisesfromthestandardrepresentationofthenumerouspaddle-wheeldecoratedsqlnets.
Inthiswork,wechoosetogiveonlyonerepresentationforeachcompound,hence4,4L1netsareherereportedassql(seeFigureS2inSupportingInformation).
Instead,thefourthmostfrequenttype(with485structuresreportedinref3)ofsingle2Dnets,the(3,6)-ckgdnet,hasbeenobservedonlyinonestructure,Zn5(bpib)2(L)4(OH)2(H2O)2{TONFUY,wherebpib=1,4-bis[2-(pyridin-2-yl)-1H-imidazol-1-yl]butaneandH2L=3,3′-methylenebis(oxy)dibenzoicacid}18as2-foldinterpenetrated.
Therhombicgeometryofkgdmakesitlessexible,hamperingentanglement;onlythepresenceofbentligandssupportsthistopologyinTONFUY(seeFigureS3inSupportingInformation).
Othertopologiesobservedinnotentangled2Dnets3areprobablylesssuitedtogiveinterlacedspecies.
Toincludeallthephenomenaobservedhere,weextendthedenitionofentanglementintroducedsomeyearsago:2c,ftogetherwiththeclassicalinterpenetrationandpolycatenationFigure2.
Netdistributionofthe7832Dentangledmotifs.
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2014,114,755775807559(parallelandinclined)viaHopflinks,weobservedmanyexamplesofentangled2Dnetswith2-loopsviarotaxanelinks.
19Aschemethatincludesallpossibleobservedandnot-yet-observedcasesisgiveninFigure6.
Themaindistinctionillustratedhereisbetweeninterpenetration(INT,leftcolumn)andpolycatenation(parallelPCATorinclinedICAT,rightcolumn).
Thesetwobasictypesofentanglementshowquitedistincttopologicalfeaturesthatarelistedinthetwocolumns.
WithinpolycatenationthedistinctlayerscaninterlaceviaHopflinkseitherinparallelfashion(alllayersareparallel)orininclinedfashion(twoormoresetsofparallellayersformingacertainnonzeroangle);thisdierencewasevidencedsincethe1990sandwaswidelydiscussedinthereviewbyBattenandRobson.
2aIntotal,thereare345interpenetrated(INT),127polycatenatedparallel(PCAT),and222inclined(ICAT)coordinationnetworks.
Theremainingstructures(notincludedintheabovescheme)comprise31Borromeanentangled(BORR),2015species(MIXED)thatcannotbestrictlyassignedtoanyofthepreviousclassesshowingmixedtypeofentanglement,and43structurescontaining2-looprings(ofthese,thereare39INT,twoPCAT,andtwoICAT).
ThepiechartillustratedinFigure7showsanalmostequaldistributionofinterpenetration(345+39=384)andpolycatenation(127+222+2+2=353),withonly5.
9%dierentphenomena(MIXED+BORR).
Polyrotaxaneentanglementvia2-loopsisalsorepresentedbyasmallsample(5.
5%).
The77structures(10%ofthewholesample)thatarerepresentedbythicklayershavemostlypolycatenatedparallelentanglement(84%),showingthatthenonplanarityofalayerfavorsparallelentanglement.
3.
1.
InterpenetrationInterpenetrated2Dlayersrepresentthemostnumerousgroup(overall384entries).
Thistypeofentanglementisgenerallycharacterizedbythepresenceof2Didenticalmotifsthatareinterlaced,sharingthesameaverageplane.
ThedegreeofinterpenetrationZisequaltothetotalnumberofsuchmotifs.
Wehavepreviouslyinvestigatedtheinterpenetrationof3Dcoordinationnetworksandhavesuggestedaclassicationrelatedtothedistinctmodesinwhichindividualidenticalmotifscaninterpenetrate,representedbytheoperationsthatgeneratethewholearrayfromasinglenet(classesI,II,andIII).
2d,8Thoughthisapproachhasapotentialheuristicvalidityandhasbeenusefullyappliedintheanalysisofinterpenetrationinmany3Dsystems,2d,14itisessentiallybasedongeometrical,ratherthantopological,criteriasinceitdescribesinterpenetrationsimplyintermsofcrystallographicsymmetryrelations(wemaycallthem"crystalclassesofinterpenetration").
Takingintoaccountthegrowingtendencytofocusinterestontruetopologicaldescriptionsoftheentanglednetworks,asevidencedbyrecentinvestigationsandnewapproaches,21wehavedecidedtoneglectherethisclassication.
ThemaximumvalueobservedforZis6,foundonlyinhcb[Ag(1,3,5-tris(4-ethynylbenzonitrile)benzene)CF3SO3]·2C6H6(ZABQIC01;22seeFigure8)reportedin1996,wellbelowtheexceptionalrecordsfoundinarecentlyreported3Dmetalorganic103-srsnetwork(54-fold,OYEYOH)23andalsoina3DorganicH-bonded103-srsnetwork(18-fold,SAYMUB01).
24Figure3.
Nineobservedplanarnets(2-periodic2D).
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2014,114,755775807560HighvaluesofZarerare(onlythree5-foldandseven4-foldcases)andthelargemajorityofexamplesare2-foldinter-penetrated(>79%).
Wemustmentionhereaninterestingcasethatdescribesauniquelinkingmodebetweentheringsofinterpenetratingmotifsinpolymericnetworks.
Inmostcases,theshortestcircuitsofindividualpairsofnetworkscatenateonlywith2-crossing[2]-catenanemotifs,equivalenttothe2-componentlinkwith2-crossing,theHopflink.
However,insix2-foldinterpenetratedstructureswithtopologysql,the4-crossing[2]-catenanemotif(equivalenttothe2-componentlinkwith4-crossingscalledSolomonlink/knot)hasbeenfound:[M(dde)(bpp)]·H2O[wheredde=4,4′-dicarboxydiphenyletherandbpp=1,3-bis(4-pyridyl)propane],withM=Cu(COKPIC),25Ni(COKPOI),25orCo(SOCYEP,26SOCYEP0125),andM(bbmb)2(Cl)(OH)]-(H2O)2[wherebbmb=4,4′-bis(benzimidazol-1-ylmethyl)-biphenyl],withM=Ni(FUYWIG)27andCu(FUYWOM)27(seeFigure9).
Suchmulticrossinglinksarerarelyobservedalsoin3Dinterpenetration;oneknownexampleisthe4-crossing[2]-catenanemotifidentiedfor2-foldquartzqtznets.
28Ananalysisofthe2DinterpenetratingnetslistedbyTOPOSshowsthepresenceofsubgroupsofstructureshavingpeculiargeometricalandtopologicalfeaturesthatmakethemwelldistinctfromtheremainder.
Onesubgroupcomprisesspecieswithlayerscontaining2-nodeloops(2-memberedrings)thatarethreadedbyspacersformingedgesofthe2Dlayers(39entriesinthelist).
Thissubgroup(wecancallthistypeofentanglement"polythreadedinterpenetration")hasbeenthesubjectofarecentreview19andwillbediscussedinmoredetailinsection3.
2.
Inthesecondsubgroup,comprising,atpresent,onlyafewspecies,theinterlacedlayersarenotcoplanarbutshowarelativedisplacementinthestackingdirection.
Byextrapolationfromthefewrealcases,wecanimagineanentirenewclassofnetworksthatcanbeconsideredascutsof3Dparallelpolycatenatedarrays(likethethreeinterlacednetsinFigure10),withanitenumbernofcatenatedlayers(n-catenation).
Whileinterpenetrationoflayersimpliesthateachmotifisinterlacedwithalltheotheronesofthearray,thisisnotthecasefortherstspeciesinFigure10,wheretheaverageplanesofadjacentlayersaredisplacedalongthestackingdirection:thisexampleatpresenthasneverbeenobserved.
Figure4.
Ninenewtopologiesobservedonlywithinentangled2Dnets;sevenareobservedwithinparallelpolycatenation(PCAT),onewithinmixedtype(bottomleft),andonewithininterpenetration(INT).
Refcodesforthenetsobservedinonlyonestructurearegiven.
Figure5.
Threedierent(non-ambientisotopic)embeddingsofKIaobservedin2Dstructures(nineentangledand69single)thatcannotbedeformedintoeachotherwithoutcrossingedges.
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2014,114,755775807561Wecanincludeinthisnewfamily[Cd2(bpt)(ip)2(H2O)4]·6H2O[wherebpt=4-amino-3,5-bis(4-pyridyl)-1,2,4-triazoleandip=isophthalate](UDIROP)29and{[Cd2(TPOM)-(hpbb)2][whereTPOM=tetrakis(4-pyridyloxy-methylene)-methaneandH2pbb=4,4′-(hexauoroisopropylidene)bis-(benzoicacid)](FAMGEH)30(seeFigure10)thatareboth2-catenatedarrays.
Anotherexampleis[Co2(bipe)1.
5(bta)(H2O)4][Co(bipe)-(bta)](H2O)0.
5[whereH3bta=benzene-1,2,3-tricarboxylicacidandbipe=1,2-bis(4-pyridyl)ethane](EWOTAM)31(seeFigure11),a3-catenatedarrayinwhicha3,3,3L5complexuniquecentralself-catenatedlayer(showninblueinFigure11)isFigure6.
(Top)Completeschemeofclassicationofentanglementinperiodicstructures.
(*)Thisconditionisdisregardedforonlyonestructure,EWOTAM;seetext.
(Bottom)Examplesofentanglementofhcbnetsshowingthedierencebetweeninterpenetrationandpolycatenation(parallelandinclined).
Figure7.
(Left)Distributionofinterpenetrationvspolycatenationin7832Dentangledstructures.
(Right)Distributionofthickandplanarlayersamongthesixtypesofentangledstructures.
Figure8.
Maximuminterpenetrationobservedin6-foldhcb[Ag(1,3,5-tris(4-ethynylbenzonitrile)benzene)CF3SO3]·2C6H6(ZABQIC01).
Figure9.
Rarecaseof2-componentlinkwith4-crossingsobservedinsix2-foldinterpenetratedsqlstructures:(left)[M(dde)(bpp)]·H2Oand(right)M(bbmb)2(Cl)(OH)](H2O)2(seetext).
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2014,114,755775807562interlacedwithtwoequalupperandlowersqllayers(showningreeninFigure11).
Itisnotpossibletospeakhereoftrueinterpenetrationsincethelayersaredierentandtheexternaltwoarenotinterlinked.
Thedicultiesinthestudyofentanglementscanproducewrongdescriptionsintheliterature:forexample,inthestructureofZn3(BIDPE)3(5-HIPA)3·4H2O[whereBIDPE=4,4′-bis-(imidazol-1-yl)diphenyletherand5-HIPA=5-hydroxyisoph-thalate](IXOHOT),32theauthorsdescribethisspeciesasacaseof"nitepolycatenation",consistingofsixcatenatedsqllayers.
Unfortunately,theirclaimthat"thisistherstreportofsixidenticalsheetspolycatenatedstilltoforma2D→2Dnetwork"iswrong;themoreusual2D→3Dparallelpolycatenationisobservedhere,accordingtoanalysiswithTOPOS.
Whenthethreeaboven-catenated(nottrulyinterpenetrated)speciesareneglected,allothercasesoftrueinterpenetrationarecomposedofidenticalcoplanarmotifsexceptfortwoexamples,([Mn(NCS)2(4,4′-bis-pyridylpropane)2]·0.
25H2O;MULFEE33andREDSEZ34),wherethetwointerpenetratinglayersareverysimilarbutcrystallographicallyindependentwithsmalldier-encesinconformationsoftheexibleligands.
Theoccurrenceofdierentinterlaced2Dmotifs,ontheotherhand,ismuchmorefrequentinothertypesofentanglements,suchasinclinedpolycatenation(seesection3.
4).
Interpenetrationofsqllayerssupportssolid-statereactionsviasingle-crystaltosingle-crystal(SCSC)transformation,from4-foldsqlto4-folddia35andguest-drivenligandexchange.
36Wecanmentionherealsothenonlinearoptics(NLO)propertieswithstrongsecondharmonicgeneration(SHG)eectofa2-foldinterpenetratedsqlspecies.
373.
2.
EntanglementsofTwo-DimensionalLayersContaining2-MemberedLoopsAcloserexaminationofthelistofinterpenetrating2DnetworksobtainedfromTOPOSrevealsthepresenceofasignicantnumberofcaseswithlayerscontaining2-memberedrings.
Theyformaspecialsubclasswithininterpenetration(wesuggestthename"polythreadedinterpenetration"),withthepeculiarfeaturethattheentanglementconsistsofthreadingofthe2-nodeloopsbyedgesofadjacentlayers(Table1).
Ifoneappliesthenormalsimplicationprocessusedinthenetworkapproachfortopologicalclassicationofthelayer,theriskistooverviewtheentanglement.
Indeed,therearemany1D,2D,and3Dframeworkscontaining2-noderingsthatarenottopologicallysignicant,butthisisnottrueinthepresentspecies.
AsclearlydiscussedforthersttimebyMa,Batten,andco-workers,38herethe2-nodeloopsmustbeexplicitlyconsidered.
Aspecialtopologicalnotationisrequiredforthesinglelayer:avertexsymbol(VS)thatincludesalsothe2-connectednodesissuggestedinsteadoftheusualVSoftheunderlyingsimplied2Dnet,andthisspecialnotationhasbeenaddedintoTOPOS.
Theseentangledspeciescanbedescribedaspolyrotaxane-likestructuresandwerepreviouslyincludedinthecasesofpolythreading.
2cTwo"older"examplesshowninFigure12havebeenknownsincethemid-1990s,butsince2007manynewfascinatingspeciesofthistypehavebeenreported.
Duringpreparationofthispaper,areview19hasappeareddescribingindetailthesespeciescontaining2-memberedloops,withinterestingcomments.
Theconceptof"nontrivialpolyrotaxane"isintroducedandadenitionisproposed.
19,39Wewillusewhenpossible(inTable1)theclassicationillustratedbytheseauthors.
Allthesespeciesareformedbytheinterlacingoflayersoffourdistincttopologicaltypesonly,illustratedinFigure13,whosesimpliedtopologiesarehcb(2,4L1)andsqlfor2,6L1,2,6L2,and2,10L1,whichdierinthepositionandnumberofthe2-nodeloops.
Inextricableentanglementsoftheselayersexhibitthepresenceofrotaxane-likelinkagesofdierenttypes,dependingonthenumberofrodsandringsinvolved.
Byanalogywiththeclassicationsuggestedformolecularrotaxanes,69wecanadoptwhenpossibleanotationlikethefollowingone:1.
1(onerod,onering),1.
2(onerod,tworings),2.
1(tworods,onering),2.
2(tworods,tworings)andsoon.
Thecasesof2-foldinterpenetration(35entriesoutof43,thelargemajorityinTable1)arealmostequallydistributedbetweenthetwostructuresIandIIshownaboveinFigure12(classiedasIIIaandIIIb,respectively,inref19).
Inthesespecies,theusuallinksarerotaxanesoftype1.
1.
Thereareonlythreerecentexceptions(DAYMEX,41ETEKUK,43andUYOHOG;61seeFigure14);thesecontainthelayers2,10L1withpeculiarstructuralfeaturessuchthatrodsofthesecondlayerarethreadedbytwoadjacentloopsoftherstlayerandviceversa.
Thus,therotaxanelinksareoftype1.
2.
Itisworthmentioningherethatthereisonlyonespecies,atpresent,containinglayersoftype2,6L2:the2-foldinter-penetratedQUQGOZ56(type1.
1rotaxane,seeFigure15).
Theexamplesof3-foldinterpenetrationincludetwospecieswith2,4L1-typelayers(WAGXAFandWAGXEJ)66andtwowith2,6L1typelayers(NUDDEW54andTONGAF60),illustratedinFigure15).
Inthetwoformercases,eachloopisthreadedbytworodsandeachrodthreadsonlyonering(rotaxanetype2.
1),whileinthelattertwocaseseachloopisthreadedbytworodsandFigure10.
Possibleinterpenetrationwiththeequivalentinterlacedlayersnotcoplanarbutwitharelativedisplacementinthestackingdirection.
Onlythe2-fold2-catenatedmotifhasbeenobserved.
Figure11.
Unique3-catenatedarraywithnonequivalentlayersobservedinEWOTAM.
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EntangledTwo-DimensionalNetworksContainingTwo-MemberedLoopsrefcodecompdformulaa,bentanglementtypeclayertopology:dsempl(2-c)linktypeeclassfyear,ref1ANARIR[Cd(bcbpy)(bpdc)0.
5Br]·7H2OINT-2fhcb(2,4L1)1.
1IIIa2011,402ANAROX[Cd(bcbpy)(bpdc)0.
5Cl]·7H2OINT-2fhcb(2,4L1)1.
1IIIa2011,403BOBGEF[Co2(1,3-bix)2(bpea)2]INT-2fhcb(2,4L1)1.
1IIIa2008,384DAYMEX[Mn4(pcp)4(bpye)(DMF)2]INT-2fsql(2,6L1)g1.
22012,415DUCFOX[Co2(btx)2(btx)(H2O)4(β-Mo8O26)]·2H2OINT-2fhcb(2,4L1)1.
1IIIa2009,426DUCFUD[Ni2(btx)2(btx)(H2O)4(β-Mo8O26)]·2H2OINT-2fhcb(2,4L1)1.
1IIIa2009,427DUCHIT[Zn2(btx)2(btx)(H2O)4(β-Mo8O26)]·2H2OINT-2fhcb(2,4L1)1.
1IIIa2009,428ETEKUK[Mn4(dbsf)4(1,4-bix)(H2O)4]·2H2OINT-2fsql(2,6L1)g1.
22011,439ETELAR[Ni(dbsf)(bbi)(H2O)2]·2H2OINT-2fhcb(2,4L1)1.
1IIIa2011,4310EVUSEU[Zn(Hapoxbda)(bpye)]·(DMA)·(DMA)xINT-2fhcb(2,4L1)1.
1IIIa2011,4411EYEYIRZn(Hcboxip)(bipy)1.
5INT-2fsql(2,6L1)1.
1IIIb2011,4512GALKIP[Ni(dbsf)(1,4-bix)(H2O)]·0.
38H2OINT-2fhcb(2,4L1)1.
1IIIa2012,4613GUBZIN[Mn2(H2O)4(btx)2(btx)(SiMo12O40)]·4H2OINT-2fhcb(2,4L1)1.
1IIIa2009,4714GUBZOT[Ni2(H2O)4(btx)2(btx)(SiMo12O40)]·4H2OINT-2fhcb(2,4L1)1.
1IIIa2009,4715GUBZUZ[Co2(H2O)4(btx)2(btx)(SiMo12O40)]·4H2OINT-2fhcb(2,4L1)1.
1IIIa2009,4716IQEJOE[Cd(cpmb)(bbi)0.
5(H2O)]INT-2fsql(2,6L1)1.
1IIIb2011,4817KEZPIP[Cd(cpmb)(bbi)0.
5(H2O)]INT-2fsql(2,6L1)1.
1IIIb2007,4918LALFOV[Fe(bipe){Au(CN)}{Au(CN)}·MeOH]INT-2fhcb(2,4L1)1.
1IIIa2010,5019MARMID[Co(oba)(bib)]·H2OINT-2fsql(2,6L1)1.
1IIIb2012,5120MUNPIV[Co(bih)(bpdc)]INT-2fhcb(2,4L1)1.
1IIIa2009,5221MUNPUH[Co(1,4-bix)(bpdc)]INT-2fhcb(2,4L1)1.
1IIIa2009,5222NEBSUI[Zn(1,4-bix)(1,4-bix)(NO3)2]·4.
5H2OINT-2fhcb(2,4L1)1.
1IIIa1997,5323NUDDAS[Zn(1,2-bbomb)(bipy)0.
5]INT-2fsql(2,6L1)1.
1IIIb2009,5424OVIDAZ[Zn(cpds)(bipe)0.
5INT-2fsql(2,6L1)1.
1IIIb2011,5525QUQGOZ[Zn3(OH)2(dhbbdc)2(bipy)(H2O)2]·H2OINT-2fsql(2,6L2)1.
1IIIc2010,5626RUBGIF[Ni(dbsf)2(bipy)]·H2OINT-2fsql(2,6L1)1.
1IIIb2009,5727SULKEQ[Zn(dbsf)2(bipy)]·H2OINT-2fsql(2,6L1)1.
1IIIb2009,5828TAHNIB[Zn2(dbsf)2(bpimb)]·H2OINT-2fsql(2,6L1)1.
1IIIb2010,5929TONFIM[Cd2(1,4-bix)2(dpb)2]INT-2fhcb(2,4L1)1.
1IIIa2008,6030TONFOS[Cd(mbd)(bpimb)0.
5(H2O)]INT-2fsql(2,6L1)1.
1IIIb2008,6031UYOHOG[Mn4(dba)4(1,4-bix)]INT-2fsql(2,6L1)g1.
22011,6132UZAWEY[Cd4(Hidc)2Cl4(bbi)2(bbi)]INT-2fsql(2,6L1)1.
1IIIb2011,6233WOCKOP[Cd(bpp)(tp)(H2O)]·nH2OINT-2fhcb(2,4L1)1.
1IIIa2008,6334WODGUS[Cd2(pca)2(bbi)]INT-2fsql(2,6L1)1.
1IIIb2008,6435YOCPEL[Mn2(p-xbp)2(p-xbp)](ClO4)2INT-2fsql(2,6L1)1.
1IIIb1995,6536NUDDEW[Zn2(1,3-bbomb)2(bipy)]INT-3fsql(2,6L1)2.
2IIId2009,5437TONGAF[Zn(obbd)(bpib)0.
5]INT-3fsql(2,6L1)2.
2IIId2008,6038WAGXAF[Zn(H2tfpbbp)(fip)]·H2OINT-3fhcb(2,4L1)2.
12010,6639WAGXEJ[Zn2(H2tfpbbp)2(nip)2]·H2OINT-3fhcb(2,4L1)2.
12010,6640NUDDIA[Zn4(1,2-bbomb)4(bpp)2]PPROThsql(2,6L1)iIVa2009,5441UHUROF[Co2(pcp)2(bpp)]·2CH3OHPCAThsql(2,6L1)jIVb2009,6742BOBGIJ[Cd4(1,4-bix)4(bpea)4]·4H2OIPROTkhcb(2,4L1)1.
1IVc2008,3843CUXTIZ[Zn(Hcboxip)(bimb)]·2H2OIPROTlhcb(2,4L1)1.
1IVc2010,68aLigandsformingthe2-loopsareshowninboldfacetype;ligandsactingasrodsareshowninitalictype.
bAbbreviationsforligands:bbi=1,1′-butane-1,4-diylbis(1H-imidazole);bib=1,4-bis(2-methylimidazol-1-yl)butane;bih=1,1′-hexane-1,6-diylbis(1H-imidazole);bipe=4,4′-ethane-1,2-diyldipyridine;bipy=4,4′-bipyridine;bpib=1,4-bis[2-(pyridin-2-yl)-1H-imidazol-1-yl]butane;bpimb=2,2′-[1,4-phenylenebis(methylene-1H-imidazole-1,2-diyl)]dipyridine;bimb=1,1′-(1,4-phenylene)bis(1H-imidazole);bpp=4,4′-propane-1,3-diyldipyridine;bpye=4,4′-ethene-1,2-diyldipyridine;btx=1,1′-[1,4-phenylenedi(methylene)]bis(1H-1,2,4-triazole);p-xbp=1,1′-[1,4-phenylenedi(methylene)]dipyridin-4(1H)-one;1,4-bix=1,1′-[1,4-phenylenedi(methylene)]bis(1H-imidazole);1,2-H2bbomb=4,4′-[1,2-phenylenebis(methyleneoxy)]dibenzoicacid;1,3-bix=1,1′-[1,3-phenylenedi(methylene)]bis(1H-imidazole);1,3-H2bbomb=4,4′-[1,3-phenylenebis(methyleneoxy)]dibenzoicacid;Hbcbpy=1-(4-carboxybenzyl)-4-pyridin-4-ylpyridinium;H2bpdc=biphenyl-4,4′-dicarboxylicacid;H2dpb=4-[(4-carboxybenzyl)oxy]benzoicacid;H2p=5-uoroisophthalicacid;H2nip=5-nitroisophthalicacid;H2pca=4,4′-methylenebis(3-hydroxy-2-naphthoicacid);H2bpea=4,4′-ethene-1,2-diyldibenzoicacid;H2cpds=6,6′-dithiodinicotinicacid;H2cpmb=3-[(4-methylbenzyl)amino]benzoicacid;H2dba=4,4′-methylenebis(benzoicacid);H2dbsf=4,4′-sulfonyldibenzoicacid;H2dhbbdc=4,4′-(1,2-dihydroxyethane-1,2-diyl)dibenzoicacid;H2mbd=4,4′-[methylenebis(oxy)]-dibenzoicacid;H2oba=4,4′-[1,2-ethanediylbis(oxy)]dibenzoicacid;H2obbd=4,4′-[oxybis(ethane-2,1-diyloxy)]dibenzoicacid;H2pcp=4,4′-[propane-1,3-diylbis(oxy)]dibenzoicacid;H2tfpbbp=N,N′-[(2,3,5,6-tetrauoro-1,4-phenylene)dimethylene]diisonicotinamide;H2tp=terephthalicacid;H3cboxip=5-[(4-carboxybenzyl)oxy]isophthalicacid;H3apoxbda=5-[2-(acetylamino)-4-carboxyphenoxy]isophthalicacid;H3idc=imidazole-4,5-dicarboxylicacid.
cINT-2f=2-foldinterpenetrated;PPROT=parallelentangledpolyrotaxane;IPROT=inclinedentangledpolirotaxane.
dNotation:(2,6L1)correspondstoa2,6-cnetwithpointsymbol22.
48.
65,(2,4L1)correspondstoa2,4-cnetwithpointsymbol2.
65,and(2,4L2)correspondstoa2,6-cnetwithpointsymbol22.
49.
64.
eRotaxanelinktype:1.
1foronerod/onering;1.
2foronerod/tworings;2.
2fortworods/tworings.
fClassicationaccordingtoBattenetal.
19gDimers.
hDegreeofcatenation2;indexofseparation1.
iHalfloops2.
1andhalfnotthreaded.
jAll2-loopsarecatenatedviaHopflinks.
kDegreeofcatenation2/2;angle31.
9°.
lDegreeofcatenation2/2;angle42.
5°.
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2.
Itmustbestressedthattheseinextricableentanglementsarecompletelydistinctfromthemoreusualtopologicalclassesdiscussedintheremainderofthisreview,thoughtheyarereminiscentofotherentanglementsoflayerswithout2-memberedloops.
Allthespeciesdescribedcanbeclassiedasexamplesof"polythreadedinterpenetration"(2D+2D→2D).
Ontheotherhand,afewotherspecialcaseshavealsobeenrecentlydiscoveredcontaining2Dlayerswith2-memberedloopsthat,viatheinvolvementoftheserings,give3Dnetworks.
Asinthecasesofpolycatenation,theyshowanincreaseofdimensionalitywithrespecttothebasicconstituentmotifs(i.
e.
,2D+2D→3D)(seeFigure6).
Intwocasesofthese2D+2D→3Dentanglements(BOBGIJ38andCUXTIZ68),thelayersinterlaceinaninclinedfashionthroughrotaxaneinteractionsoftype1.
1.
Twosetsofparallel2Dlayersoftype2,4L1crossatanangleof31.
9°forBOBGIJand42.
5°forCUXTIZwithpolythreadingtoproducethe3Darray.
Inbothcases,allthe2-loopsarethreadedbyrodsoftheinclinedlayerswhileonlyhalfofthesingleedgesareinvolvedinthreading.
Wecandescribethesecasesas"inclinedentangledpolyrotaxanes"(IPROT,seeTable1).
Indeed,thetwospeciesshowsomedierencesifweconsiderthedensityofentanglement,sinceinBOBGIJeachwindowofalayerisinterlacedwithtwolayersoftheinclinedset(andviceversa),whileinCUXTIZeachwindowofalayerisinterlacedwiththreelayersoftheinclinedset,asshowninFigure16.
AquitedierentsituationisobservedinNUDDIA.
54Thetopologyofthe2Dlayersisofthe2,6L1typebutwithtwoorientationsoftheloops(showninredandyellowinFigure17).
Theindividuallayersareentangledwithtwoothers(aboveandbelow)inaparallelfashion,givinganintriguing2D+2D→3Darchitecturethatresemblesthecasesofparallelpolycatenation.
Here,however,thelinksaretwo-rodrotaxanes(oftype2.
1)thatinvolveonlyhalfoftheloops(theredonesinFigure17)thatarethreadedbyonerodoftheupperandonerodofthelowerlayer.
Allthesingleedgesofthelayersareusedinthesethreadinginteractions.
Thisuniqueentanglementcanbedescribedasa"parallelentangledpolyrotaxane"(PPROT,seeTable1),withanindexofseparationIs=1(seesection3.
3forthedenition).
Also,UHUROF67isuniqueinthatthe2-memberedloopsofits2,6L1-typelayersgiveHopflinkswiththeloopsoftwoadjacentlayers(aboveandbelow),thusresultinginaparallelpolycatenated3Darray,withindexofseparationIs=1anddegreeofcatenationDoc=2(seesection3.
3fordenition).
Thisismadepossiblebythefactthatthelayersstackwithmutualrotation,inanABABsequence(seeFigure18).
703.
3.
ParallelPolycatenationTheresultsoftheanalysisusingTOPOSshowthatthereisagroupof127casesthatexhibitparallelpolycatenation;thatis,the2Dlayersareinterlacedinaparallelfashionbystackingwithosetoftheiraverageplanes.
Thistypeofentanglementisessentiallymadepossiblebythefactthattheindividuallayersdisplayacertainthickness.
Therearetworeasonsfortheoccurrenceofthicksheets:theyaremarkedlyundulatedversionsoftheplanar2DlayersillustratedinFigure3ortheyaremultiplelayers(rigorously2-periodic3D),likethoseshowninFigure4.
Theanalysisofthedistributionoftopologiesrevealsthatthethicklayers(multiplelayers)haveamarkedpreferencefortheformationofentanglementswithparallelpolycatenation(85%;seeFigure7).
Thedominanttopologyinthistypeofentanglementissql(54outofthe127examples),butthethicklayersrepresentca.
50%ofallthecases(seeFigure7).
Toachieveabetterrationalizationofthesesystems,wehaveintroducedinapreviouspaper2canindexofthe"degreeofcatenation"(Doc),denedbythenumberofmotifsnentangledtoeachsinglemotif;moreover,wehavealsosuggestedtoestablishwithinparallelpolycatenationthenumberofmotifsthatmustbe"removed"inordertoseparatethewholearrayintotwodistinctparts(indexofseparation,Is).
Inalmostallcases(withonlyveexceptions)weobserveDoc=2andIs=1;thatis,eachFigure12.
Twooldestexamplesofentanglementofpolyrotaxane-likestructuresobservedinthe1990s:NEBSUI53andYOCPEL.
65Figure13.
Fourdierentlayertopologiesobservedinpolyrotaxane-likestructures.
Figure14.
Uniquerotaxanetype1.
2(onerod,tworings).
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2014,114,755775807565layeriscatenatedwithothertwo(theupperandlowernearestneighbors)andthearraycanbedividedintotwohalvesbyeliminationofonelayer.
Itisworthmentioningbrieytheseveexceptionalcases.
In[Cu(I)2Cu(II)(bipy)2(pydc)2]·4H2O[wherebipy=4,4′-bipyr-idineandpydc=pyridine-2,4-dicarboxylate](WUVBUK71),theindividualmotifsarehcbhighlyundulatedlayers(seeFigure19)thatarecatenatedtofouradjacent(twoupperandtwolower)layers,resultinginDoc=4andIs=3.
Ontheotherhand,[Co5(bipe)9(H2O)8(SO4)4](SO4)·14H2O[wherebipe=1,2-bis(4-pyridyl)ethane](MEBBIE72)iscom-Figure15.
Threeexamplesofinterpenetratedpolyrotaxane-likestructureswithdierentrotaxanetypeofentanglementsofthe2-loops.
Figure16.
Twoexceptionalexamplesofinclinedpolythreadedentanglements.
Figure17.
Uniqueexampleofparallelpolythreadedentanglement.
Figure18.
UniqueexampleofparallelpolycatenationviaHopflinksof2-loops.
Figure19.
Exceptionalcaseofparallelpolycatenationobservedin[CuI2CuII(bipy)2(pydc)2]·4H2O,showingDoc=4withthefourredlayerscatenatedwiththereferenceone(blue)andtheremovalofthreenumberedlayersresultinginIs=3.
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2014,114,755775807566posedofveryhighve-deckedmultiple2Dlayerswithacomplexuniquetopologythatcanbedescribedasave-layersectionofthechiralthree-dimensionalfour-connectedframeworkof(75.
9)-qzdtopology.
ThesemultiplelayersareinterlacedinparallelfashionwithfoursuchadjacentlayerswithindexesDoc=4andIs=2(seeref72fordetailedgures).
Twootherexamplesexhibitahighdegreeofcatenation(Doc=4,Is=2):,Cu4(dicyanamide)4(bipy)3(MeCN)2(LOT-QUG73)and[Ag3L2][PF6]3·1.
6THF·0.
5C6H6·CH2Cl2[whereL=tetrakis(4-cyanophenyl)silane](NORDAZ,74therstcaseofparallelpolycatenation,reportedin1997).
Bothshowthesame3,4L88topologyoftheirthicksheetsthatarebilayersrepresentingacutofdiamonddia(seeFigure20).
Bilayerswiththistopologyarerelativelycommoninthistypeofentanglement.
Therearevecases(XODJOQ,75BOQSEG,76BURGAX,77OKEJIY,78andWAVTEU79)allhavingDoc=2andIs=1,veryprobablyduetothedecreaseofcagedimensions.
AspecialcaseisthatofWUJDIO,80apuzzlingspeciesshowingparallelpolycatenationofKIathicklayers,withDoc=2butIs=2,whichwillbediscussedlater.
Arecentarticle81illustratesararebreathingbehaviorsupportedbyparallelpolycatenation.
Manydynamicporoussystemshavebeencharacterizeduptonowevidencingthatdierentmechanismsareattheoriginofthisphenomenon,alsocalledgate-opening(withstepwiseisotherms).
Interestingly,thesetypesofnewadsorptionproleswererstrecognizedforstacked2Dcoordinationlayers.
82In2001,LiandKaneko82aintroducedtheterm"gateopeningpressure"toexplainthegasadsorptionisothermsmeasuredonthestackedsquarelayers[Cu(bipy)2(BF4)2](bipy=4,4′-bipyridine)thatunusuallyshowednoadsorptionbelowthe"gatepressure"valueandasteepincreaseatthisvalue.
83InthesameyearKepertandco-workers84reportedanextensivegasandvaporsadsorptionstudyontheexibleinterdigitatedlayersof(82.
10)-KIatopology[Ni2(4,4′-bipyridine)3(NO3)4]showingstepadsorptioniso-therms.
Aftertheseearlyreports,manyotherexamplesofexible2Dcoordinationnetworkshavebeenreported.
85Ithasbeenwelldocumentedthatthedynamisminstacked2Dcoordinationnetworksisassociatedwithexpansion/shrinkageorslidingofthelayersaswellasthebreathingphenomenon;itfollowsthat2Dlayerspolycatenated(undulatedorthick)maybegoodcandidatesforsuchdynamicbehavior.
863.
4.
InclinedPolycatenationThisisaquitelargefamilyofpolycatenated2Dframesthatinclude222cases,manyofwhichwerealreadyreviewedindetailpreviously.
2acItisthesecondlargestgroupafterthatofinterpenetratedarrays(29%vs49%)asshowninFigure7.
Themajorityofthesespeciesconsistoftwoidenticalsetsof2Dparallellayersspanningtwodierentstackingdirections.
Theyarecharacterizedbyanincreaseofdimensionality(2D→3D)andeachindividualmotifiscatenatedwithaninnitenumberofotherinclinedlayersbut,obviously,notwithalltheframescontainedinthe3Darray.
Alsoforthistypeofentanglementwecandenea"degreeofcatenation"(Doc),asymboloftype(a/b/.
.
.
),wherea,b,.
.
.
arethenumbersof"external"ringscatenatedtoasingleringintherst,second,.
.
.
,motif,inorderofincreasingvalue.
2cAnalysisofthetopologiesofsingle2Dmotifsshowsthatalimitednumberofnetsisobserved:sql(159),hcb(45),fes(10),3,4L13(4),4,4L28(1),andthreewithlayersofdierenttopologies(seebelow).
The3,4L13and4,4L28topologiesareillustratedinFigure21.
Cu4(ODPA)2(bpye)4(H2O)10·2H2O[whereH4ODPA=3,3′,4,4′-oxidiphthalicacidandbpye=4,4′-ethene-1,2-diyldipyridine](WAVVIA87)isauniquespeciesexhibitinginclinedpolycatenationofthicklayers(of4,4L28topology),atdierencefromwhatobservedinparallelpolycatenationwhereinterlockingofthicklayersisacommonfeature.
3,4L13isaplanarnetobservedforthefourisomorphousM(MPDCO)(TPB)0.
5(H2O)·(H2O)x,whereMPDCO=6-methylpyridine-2,4-dicarboxylicacidN-oxide,TPB=1,2,3,4-tetra-(4-pyridyl)butane,andM=Co(JITHUQ),Ni(JITJAY),Zn(JITJEC),orCd(JITJIG).
88Becausethedominanttopologyofthelayersissql(morethan70%),particularattentionhasbeendevotedsincethebeginningtoclassicationofthedierentwaysofinterlockingoftwoindependentsets.
Threepossiblearrangementshavebeensuggested,withalargelyacceptednotation:parallelparallel(pp),paralleldiagonal(pd),anddiagonaldiagonal(dd),dependingontherelativeorientationoftheframes.
2c,89AmoredetailedandautomaticclassicationispossiblewiththenewFigure20.
Thicklayer3,4L88anditsobservedparallelpolycatenationinsevenstructures.
Figure21.
Raretopologiesofinclinedpolycatenationobservedinvestructures.
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2014,114,755775807567topologicalanalysisofHopfringnets21thatwillbereportedinfuturepapers.
Withintheinclinedpolycatenationcategory,manypeculiarsituationsareobservedthatdeservegreaterattention.
Thisisduetothepossiblepresenceof(I)layersofdierentnature(i.
e.
,dierentbytopologyorbychemicalcompositionorevenonlybyligandconformationthat,moreover,canbepresentindierentratios),(II)morethantwointerlacedparallelstackingsets,or(III)unusualvaluesoftheDocindexes.
Insomecases,acombinationofmoreoftheabovefeaturescanbeobservedtogether.
ParticularlyintriguingarethethreecasesexhibitinginclinedpolycatenationoflayerswithdierenttopologiesthatareillustratedinFigure22.
EHOVON,90Ni2(btec)(azpy)2(H2O)6]-[Ni2(btec)(azpy)(H2O)4][whereH4btec=1,2,4,5-benzenete-tracarboxylicacidandazpy=4,4′-azobis(pyridine)],containshcband3,4L13layersinratio1:1andwithDoc=1/1.
Theothertwocases,[Ni(azpy)2(NO3)2]2[Ni2(azpy)3(NO3)4](MA-HYID91)and[Zn(tp)(1,3-bix)]2[Zn2(tp)2(1,3-bix)](GIM-GEP92)[wheretp=terephthalateand1,3-bix=1,3-bis-(imidazol-1-ylmethyl)benzene],bothcontainsqlandhcbinratio2:1.
ThisdierentratioaectsthevaluesofDoc,whichare1/2and1.
5/3,respectively.
ThelatternonintegervalueofDocarisesfromtheuniqueentanglementinGIMGEP:thesqlarerepresentedbytwoindependent4-ringsthatintotalcatenatewiththree6-ringsofhcb(3/2=1.
5),whiletheunique6-ringofthehcbcatenateswiththree4-ringsofthreesql(3),resultinginDoc1.
5/3.
Sixspeciescontaininterlacedlayersofthesamesqltopologybutdierentchemicalcomposition(MOVSEW,93SARFOH,94andVIRYIF95)orligandconformation(MUPZON,96EWAX-UV,97andKOLPEH98).
Indetail:(1)VIRYIF:95Doc1/1,ratio1:1,[Cu(bbi)2][Cu(bbi)V4O12],wherebbi=1,1′-(butane-1,4-diyl)bis(imidazole)(2)MOVSEW:93Doc1/2,ratio1:1,rectangularandsquaresql,[Cu2(5-HIPA)2(4,4′-bipy)2(H2O)2][Cu3(5-HI-PA)2(pyridine-2-carboxylate)2(bipy)2(H2O)4],where5-HIPA=5-hydroxyisophthalateandbipy=4,4′-bipyridine(3)SARFOH:94Doc0.
5/1,ratio1:2,rectangularandsquaresql,[Co2(pico)2(4,4′-bpy)(H2O)2][Co(pico)(4,4′-bpy)]2,wherepico=3-hydroxypicolinate(4)MUPZON:96Doc1/2,ratio1:2,[Ni(bipe)(ip)(H2O)]-[Ni(bipe′)(ip′)(H2O)]2,wherebipe=1,2-bis(4-pyridyl)ethaneandip=isophthalate(5)EWAXUV:97Doc2/2,ratio1:1,planarsqlwithdierentplanarsymmetryc2mmandp4gm,[Cu(1,4-bix)2(SO4)][Cu(1,4-bix′)2(SO4)],where1,4-bix=1,4-bis(1-imidazolylmethyl)-benzene(6)KOLPEH:98Doc1/1,ratio1:1,planarandundulatedsql,[Zn(dbsf)(bimb)][Zn(dbsf′)(1,2-bix′)],whereH2dbsf=4,4′-dicarboxybiphenylsulfoneand1,2-bix=1,2-bis(1-imidazolylmethyl)benzeneAnotherpeculiarsituationconsistsofthepresenceofmorethantwo(asusual)crossingsetsofparallellayers,summarizedinFigure23.
Theanalysisrevealsthatsevencasesshowthisfeature.
Fiveofthemarecomposedofthreesetsofsqlwhosestackingdirectionsliecoplanar;fourofthesehaveDoc2/2/2whileDoc2/2/4isobservedonlyfor{[Ni-(bipe)2(H2O)2]2[Ni2(bipe)3(H2O)6][Ni2(bipe)3(H2O)6]}-(SO4)6[wherebipe=1,2-bis(4-pyridyl)ethane](EJAXOC99),whichpresentsthethreesqlintheratio2:1:1withsquare:rectangular:rectangularwindows.
Thesimplerexampleof[Ni(4,4′-bipyridine)(4-carboxylatocinnamato)](VUX-XOC100)isillustratedinFigure23).
Theothertwocases(outoftheseven)aredierent:[Fe(bpb)2(NCS)2],wherebpb=1,4-bis(4-pyridyl)butadiyne(QOVYEF101),containsthreesetsofsqlthatstackinthreeperpendiculardirectionswithratio1:1:2,givingaDocof3/5/5;and[Co2(4,4′-azopyridine)3(NO3)4](REBWUQ102)exhibitsfourequalsetsofhcb,whosestackingFigure22.
Theonlythreecasesexhibitinginclinedpolycatenationoflayerswithdierenttopologies.
Figure23.
Inclinedpolycatenationwithmorethantwocrossingsetsofparallellayers.
ChemicalReviewsReviewdx.
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2014,114,755775807568directionsaredisposedarounda4-foldcrystallographicaxis,givingaDocof3/3/3/3(seeFigure23).
WecannowbrieyexaminethevaluesoftheindexDoc.
The"normal"caseswithDoc=1/1appearfor123structuresover222,andmarkedlydecreaseuponpassingtoDoc=2/2(71structures)andtoDoc=3/3(12structures).
Withinthe"normal"casesthesqltopologyisdominant(86%),whileinthecaseswithDoc=2/2thesqlandhcbtopologiesarealmostequallypopulated.
WithDoc=3/3,thefestopologyisobserved10timesversusoneinstanceeachforhcbandsql.
AllthreedistincttypesareshowninFigure24.
Thetrendcouldberationalizedbyconsideringthattheincreaseindegreeofcatenationcanbefavoredbyanincreaseofthedimensionsofthenetwindowsuponpassingfromsquares(sql)tohexagons(hcb)andnallytooctagons(fes),onmaintainingthesameedge.
ItisworthmentioningthatthereisonlyonecasewithDoc=4/4:[Zn2(SO4)2(2,6-ndc)(L)][where2,6-H2ndc=2,6-naphthalenedicarboxylicacidandL=N,N′-bis(pyridin-4-yl)hexanediamide](OTUYAE103),basedonsqllayerswithlargerectangularmeshes.
Particularlyintriguingisthestructureof(CuCN)20(piperazine)7(NIMQOQ;104seeFigure25),withastrangeDocvalueof1/6thatisbasedontheinclinedpolycatenationoftwosetsofhcblayersofquitedierentnatureanddimensions.
OnelayercontainsverylargeringsconsistingofCu18(CN)16(piperazine)2macrocyclesthatarecatenatedbysixlayersofthesecondtype,composedofhexagonalCu6(CN)4(piperazine)2units.
ThoughgenerallyallthewindowsofalayershowthesamevalueofDoc,afewexceptionshavealsobeenobservedandareillustratedinFigure25.
WehavealreadymentionedGIMGEP,92withDoc=1.
5/3,amongthethreecaseswithlayersofdierenttopology(seeFigure23).
Moreover,wecanciteSARFOH,94whereonlyhalfthesquarewindowsofonesetarecatenatedandhencewecanreasonablyassumeDoc=0.
5/1,andMUPZON,96wherethedierentconformationoftheligandcreatesadierentratioofthesqlwithrectangularshape,givinganasymmetriccatenationwithDoc=1/2.
Similarly,in[M(terephthalato)-(bispyridylpropane)],whereM=Co(BIYFAR)105orZn(GIDMUC),106bothwithundulatedsqltopology,alllayershavehalfthesquarewindowsdoublycatenatedandtheremainderonlysinglycatenated,henceDoc=1.
5/1.
5.
Theinclinedpolycatenationcategoryshowsmanyexampleswithinterestingmagneticproperties.
Kepertandco-workers107studiedaseriesofironsqlwithDoc=1/1exhibitinginclinationanglesbetweenlayersintherange53.
590°.
Twocobaltcompoundswithsqltopologyalsoshowsimilarproperties:SARFOH,94discussedpreviously,andUNEGEA,108withDoc=2/2.
Otherinterestingpropertieshavebeenobservedinthisclass,veryprobablyduetotheexibilityoftheentanglement:Figure24.
Topologiesobservedin10casesofinclinedpolycatenationwithDoc=3/3.
Figure25.
Inclinedpolycatenationexampleswithunusualvaluesofdegreeofcatenation.
HighlightedinredareringsnotcatenatedinSARFOHandthetworingswithdierentcatenationinBIYFARandGIDMUC.
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2014,114,755775807569breathingbehavior,109solidstatereaction[2+2]photo-dimerizationbetweentheinclinedsqlnets,110andsingle-crystaltosingle-crystalguestexchangeinhcbwithDoc=2/2.
1113.
5.
BorromeanLinksMolecularringscangiveinextricableentanglementsnotonlyviatopologicalHopflinks;analternativewayinvolvingatleastthreeclosedcircuitsatatimeisrepresentedbytheBorromeanlink(seeFigure26).
TheconstructionofmolecularBorromeanringshasbeenrealizedbyStoddartandco-workers112withanall-in-onesyntheticstrategy.
TheexistenceofBorromeanlinks(insteadoftheusualHopflinks)inentangledcoordinationframeworkswasnoticedsomeyearsago.
2c,20Thisndinghasprobablystimulatedinvestigationsonthesubject,andsincethenseveralnewexampleshavebeendiscoveredintheareaofcoordinationpolymers(seeTable2).
ManystudieshavealsobeendevotedinrecentyearstotherationalsynthesisofBorromeannetworksoforganicmolecularspeciesviaweakcontacts,includingavarietyofsupramolecularinteractionslikehydrogenbonds,halogenbonding,π···πstacking,andM···M(metallophilic)interactions.
TobuildBorromeanstructures,thehoneycombnet(hcb)seemsessentialinanysyntheticstrategy.
113InTable2wereportonlythespeciessustainedbycoordinativebondsandbelongingtotherealmofcoordinationframeworks.
Theseinclude2D(15cases)and3D(12cases)Borromeanentanglements.
Fourotherexamplesexhibitingpeculiarfeaturesarealsolisted;moreover,twocaseshavealsobeenrecognized,forthersttime,tocontain5-Borromeancoplanarentanglementswithacomplex"non-Brunnian"link(seebelow).
135Alltheindividuallayersshowthehcbtopology,andasiswell-known,20inthesearrays(exceptinMUHVOBandMUH-VOB01)125eachlayerisentangledwithtwoothers(one"above"andone"below").
Adjacentlayers,however,arenotcatenatedbutarelinkedviaBorromeanlinks,inwhichnotwoindividualringsareinterlocked.
Theselinkscanproduce2DBorromeanentanglements(2D→2D)(Figure27)aswellas3Dentanglements(2D→3D)(Figure28).
Inthe2Dentanglementsanitenumberoflayers(n≥3)areinterlockedbymeansofn-Borromeanlinks,whileinthe3Dentanglementsthewholearrayrepresentsaninnitecaseofn-Borromeanlinks(Figure28).
Chainsofringsofthiskindaresuchthatnooneringiscatenatedtootherones(Doc=0)butcannotbeseparated.
Inbothcaseswehavetwopossibilities:(i)thearraycanbecompletelyseparatedintothecomponentmotifsbyeliminatingonlyonelayer,thatis,itpossessesthe"Brunnian"property(wedenethisasan-Brunniansystem);136or(ii)thearraydoesnotshowtheBrunnianproperty,thatis,theeliminationofonemotifdoesnotseparatethesystemintofreecomponents(asinan-BorromeansystemlikethechaininFigure28,whereoneeliminationsplitsthesystemintotwohalvesbutleavesalltheothermotifsinextricablyentangled).
ObviouslythreeBorromeanrings,aswellasany3-fold2DBorromeanarray,musthavetheBrunnianproperty(Figure27).
Themajorgroup(15entries)inTable2consistsof2D3-foldentangledBorromeanlayers.
Theyareusuallycharacterizedbythepresenceofmoderatelyundulatedhoneycomblayers(ofacertainthickness,rangefrom3.
0uptoca.
9.
6);thisstructuralfeatureisveryprobablythemainfactorthatfavorstheformationof2Dversus3Dsystems,whichalwaysexhibithighlyundulatedlayers(rangefrom9.
4uptoca.
19.
8)(seebelow).
ItisworthmentioningherethecaseofDOJFUD,(CuCl)2(η2,η2-p-divinylbenzene),reportedmanyyearsagoin1985.
137OuranalyseshaverevealedthatifweconsiderasnodestheCu3Cl3hexagonalunits[CuCledgesof2.
275(3)and2.
323(3)]andasspacersthe(Cu-η2bonded)p-divinylbenzenemolecules,weobtainhcblayersthatgivea2DBorromeanentanglement.
Tothebestofourknowledge,thisistheoldestexampleofsuchentanglementthatwewereabletondwithincoordinationnetworks.
However,anyCu3Cl3hexagonissuperimposedonanidentical(butrotated)unit,thusgivingahexagonalprismaticCu6Cl6clusterwithinterhexagonaldistances[CuCl2.
757(3)]muchlongerthantheanalogousintra-hexagonalcontacts.
Whentheseinteractions(ca.
0.
4shorterthanthesumofvanderWaalsradii)arealsotakenintoaccount,thewholearraybecomesaunique2Dself-catenatedcomplexsheet.
Duetothisuncertainty(orarbitraryselection),wehavedecidedtoexcludeDOJFUDfromTable2.
Thehoneycombnetsofthese2Dlayersareratherdistortedwithrespecttotheidealplanargeometry,andinsteadachairconformationofthe6-ringisobserved(seeFigures27and28).
Inprinciple,2DlayersofanytopologycouldbelinkedintoBorromeanentanglements,andsometheoreticalexamplesinvolvingmotifswithsqlwindows(likeladders)werepreviouslysuggested.
20Thoughallthereportedcases(withincoordinationpolymers)containlayerswiththesamehcbtopology,anoteworthyspecieshasbeenrecentlydescribed:[Ni-(H2O)4(Bpybc)(phthalate)]·9H2O[whereBpybc=1,10-bis(4-carboxybenzyl)-4,4′-bipyridinium](UGUGAF138),whichissustainedbyH-bondsjoiningdimericNi2nodesandrevealstheBorromeaninterlacingofthreesqllayers(seeFigure29).
Inthe3DBorromeanentanglements(12entries),theadjacenthighlyundulatedlayersaredisplacedalongthestackingdirection,adierencefromthe3-fold2DBorromeanarrayswhereallthelayerssharethesameaverageplane.
Thelayersarecharacterizedbyhexagonalwindowsinthechairconformationwithverylongedges;itcomesoutthattheydisplayapronouncedthickness(seeTable2)thatcanfavortheinterlacingofadjacentlayers.
Asinthecaseofthe2DspeciesYUXGOO,126BorromeanentanglementsseemfavoredbythepresenceofargentophilicAg···Agshortcontacts(wellbelowthesumofthevanderWaalsradiioftwoAgatoms),asevidencedinthe3DHOFXOPandHOFXUV.
128InthesespeciesthesilvernodesshowinterlayerAg···Agunsupportedinteractionsof2.
934(2)and2.
946(2),respectively.
Whentheseargentophiliccontactswithinthebondingschemearealsotakenintoaccount,indeed,asingle3Darrayresults(assuggestedbytheauthors):theuniqueself-catenateddia,anonambientisotopicembeddingofthediamondoidnet.
2e,h,20Thestructureof3DWIYMIA131isexceptionalinthattheedgesofthehcblayersare"rotaxane-like"unitswiththreadedcucurbiturilmolecularbeads.
ItisthereforeauniqueexampleofFigure26.
Twopossibleinextricableentanglementsforathree-componentlink:ontheleft,theringsareentangledincouplesbyHopflinks(asobservedin6-ringsfroma3-foldinterpenetratedhcb);ontheright,aBorromeanlinkispresented.
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BorromeanLinkedArraysrefcodecompdformulaaentanglementrecognizedbyauthors(Y/N)layertopology,stackingdirection,nodeedgeofhcb();thicknessb()spacegroupyear,ref1DAPPAN{[Ni(hatcd)]3(tcba)2}BOR(2D→2D)Yhcb,[001],tcba318.
12;7.
05R32012,1142GUWXIF{Ni(cyclam)]3(tcpeb)2}·6py·4H2OBOR(2D→2D)Nhcb,[102],tcpeb324.
90and25.
08;3.
43P21/c2003,1153ICIWOG[Cu(tmeda)]2[Au(CN)2]3ClO4BOR(2D→2D)Nhcb,[001],Cu10.
12and10.
20;6.
78R322001,1164IWENII[Zn(bmb)(tp)2·3H2OBOR(2D→2D)Yhcb,[010],Zn11.
12,14.
69,and11.
00;5.
78P12011,1175LIKBIR[WOS3Cu3(bipy)3]IBOR(2D→2D)Yhcb,[001],WOS3Cu3cluster15.
27;8.
80R3c2007,1186NEQDET[Ag2(bismin)3](CF3SO3)2BOR(2D→2D)Yhcb,[001],Ag14.
62,3.
22P32006,1197PUNRUM[Zn2(bppu)3](SO4)2·xH2OBOR(2D→2D)Yhcb,[001],Zn17.
81,9.
47R32010,1208RESHUT[Hg1I2(bippyr)Hg2I2(bippyr)0.
5]BOR(2D→2D)Yhcb,[011],Hg115.
55,22.
42,and20.
18;8.
92P12006,1219SAVCAU[Ag2(bismin)3](BF4)2BOR(2D→2D)Yhcb,[001],Ag14.
30;3.
06P32005,12210TANJEZ[(Cu4I4)2(biethiop)3(H2O)2]·4H2OBOR(2D→2D)Nhcb,[001],Cu4I4cluster19.
31;9.
58R3c2011,12311WOCXIW[Ag2(ethapu)3](NO3)2·2MeCN·xSBOR(2D→2D)Yhcb,[001],Ag16.
39and16.
04;3.
40C2/c2008,12412WOCXOCAg2(ethapu)3](NO3)2·7H2OBOR(2D→2D)Yhcb,[001],Ag16.
39and16.
04;3.
81P21/c2008,12413,14MUHVOB/01[Pb2(obed)2(bipy)]BOR5f(2D→2D)Nhcb,[100],Pb12.
31and17.
95;5.
14P21/c2009,12515YUXGOO[Ag2(bisox)3](ClO4)2BOR(2D→2D)Yhcb,[001],Ag15.
14;3.
00cP32010,12616AHIDEA[Ag2(bipycox)3OH][ClO4]·2.
5H2O3DBOR(2D→3D)Nhcb,[001],Ag18.
54,18.
72,and19.
08;16.
61P322002,12717HOFXOP[Ag2(H2bisalic)3](NO3)23DBOR(2D→3D)Nhcb,[001],Ag12.
88;9.
41dR31999,12818HOFXUV[Ag2(H2bisalic)3](ClO4)23DBOR(2D→3D)Nhcb,[001],Ag12.
13;9.
49dR31999,12819KAVDAN[(bpybc)3Mn2(H2O)6](OH)4·15H2O3DBOR(2D→3D)Nhcb,[001],Mn22.
19;19.
74R32005,12920KAVDER[(bpybc)3Ni2(H2O)6](OH)4·15H2O3DBOR(2D→3D)Nhcb,[001],Ni21.
86;19.
37R32005,12921KAVDIV[(bpybc)3Co2(H2O)6](OH)4·15H2O3DBOR(2D→3D)Nhcb,[001],Co22.
00;19.
48R32005,12922UZAZUR[Zn4(bpybc)6(H2O)12](OH)8·9H2O3DBOR(2D→3D)Nhcb,[001],Zn22.
03;19.
67R32011,13024YANWOB[Eu4(bpybc)6(H2O)9(SO4)3]·(OH)6·51.
5H2O3DBOR(2D→3D)Yhcb,[001],Eu22.
22;19.
54R32012,13225YANWUH[Mn4(bpybc)6(H2O)12](tp)3·(OH)2·30H2O3DBOR(2D→3D)Yhcb,[001],Mn22.
10;19.
82R32012,13226,27YANXAO/01[Mn2(bpybc)3(H2O)6](SO4)2·21H2O3DBOR(2D→3D)Yhcb,[001],Mn22.
32;18.
44R32012,13228GIQGAP{[Ag3(tibimt)2][Ag2(tibimt)2)]}(SbF6)5·CHCl3·H2O2D+2DBOR+2DYFor2DBOR:hcb,[001],tibimt.
For2D:hcb,[001],tibimtandAg.
For2DBOR:19.
89;8.
88.
For2D:10.
67;2.
88.
P63222007,13329GIQGET{[Ag3(tibimb)2][Ag2(tibimb)2)]}(SbF6)5·1.
5H2O2D+2DBOR+2DYFor2DBOR:hcb,[001],tibimb.
For2D:hcb,[001],tibimbandAg.
For2DBOR:19.
95;8.
76.
For2D:10.
81;3.
13.
P63222007,13330ISAROK[Ag2(bisox)3](BF4)2·1.
2Et2O2DBOR/cageYhcb,[001],Ag14.
72;3.
06eP63/m2011,13431YUXGUU[Ag2(bisox)3](ClO4)2·1.
2Et2O2DBOR/cageYhcb,[001],Ag14.
76;3.
04fP63/m2010,126aAbbreviationsforligands:biethiop=4,4′-bis(ethylthiomethyl)biphenyl;bippyr=N,N′-bis(4-pyridylmethyl)pyromelliticdiimide;bipy=4,4′-bipyridine;cox=N,N′-Bis(3-pyridinecarboxamide)-1,6-hexane;bismin=1,4-bis[(2-methylimidazol-1-yl)methyl]benzene;bisox=1,4-bis[(3,5-dimethylisoxazol-4-yl)methyl]benzene;bmb=1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene;bppu=N,N′-bis(3-pyridyl)-p-phenylenebis(urea);CB=cucurbit[6]uril;cyclam=1,4,8,11-tetraazacyclotetradecane;ethapu=L1=N,N″-ethane-1,2-diylbis(3-pyridin-3-ylurea);hactd=3,10-bis(2-uorobenzyl)-1,3,5,8,10,12-hexaazacyclotetradecane;tibimb=1,3,5-tris{4-[(2-methylbenzimidazol-1-yl)methyl]phenyl}benzene;tibimt=2,4,6-tris{4-[(2-methylbenzimidazol-1-yl)methyl]phenyl}-1,3,5-triazine;tmeda=N,N,N′,N′-tetramethylethylenediamine;H2bisalic=N,N′-bis(salicylidene)-1,4-diaminobutane;H2bpyab(NO3)2=N,N′-bis(4-carboxyphenyl)-1,4-diammoniobutanedinitrate;H2bpybcCl2=1,1′-bis(4-carboxybenzyl)-4,4′-bipyridiniumdichloride;H2obed=3,3′-[oxybis(ethane-2,1-diyloxy)]dibenzoicacid;H2tp=terephthalicacid(1,2-benzenedicarboxylicacid);H3tcba=tri(4-carboxybenzyl)amine;H3tcpeb=1,3,5-tris[2-(4-carboxyphenyl)-1-ethynyl]benzene;Et2O=diethylether;py=pyridine.
bThicknessisevaluatedasthedistancebetweenthetwoplanespassingthroughthenodesofthehcblayer.
cAg···Ag=2.
999.
dWithAg···Aginteractionsself-catenateddia.
eAg···Ag=3.
06and3.
32.
fAg···Ag=3.
04and3.
32.
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2014,114,755775807571"Borromeanpolyrotaxane",unnoticedbytheauthors(Figure30).
Fourspeciescontaining2DBorromean3-foldentangledlayersshouldbediscussedseparatelybecausetheyexhibitparticularandfascinatingadditionalstructuralfeatures.
InthepairGIQGAPandGIQGET,133therearetwodistincttypesofhcbnetworksinthesamecrystal:oneisasinglehcbnetwithshorteredgesandratheratconformation,whilethesecondonehaslongeredgesandachairconformationandisinvolvedina3-foldBorromeanentanglement.
ThecrystalpackingconsistsofstackingoftheBorromeanlayersintercalatedbytwosinglelayersthatareplacedface-to-faceonthetwosidesoftheBorromeanentanglements,thusgiving"sandwichedBorromeansheets"(Figure31).
Thesetwospeciescouldbealsoincludedinthetableofmixedentanglementsdiscussedinsection3.
6.
Anotherpairof(verysimilar)compounds,ISAROK134andYUXGUU,126showinterestingstructuresconsistingof2DBorromeanlayersintercalatedbyAg2L3cages(withthesamecompositionofthehcblayers)thatjoinadjacententangledsheetsviaweakargentophiliccontacts.
Pillaringof2DBorromeansheetsisalsoobservedin[Cd3(bfcs)3(tttmb)2(H2O)4]·8H2O[wheretttmb=1,3,5-tris(1,2,4-triazol-1-ylmethyl)-2,4,6-trime-thylbenzeneandH2bfcs=1,1′-bis(3-carboxy-1-oxopropyl)-ferrocene](FUWVUP)139withinterlayerferrocenylbridges.
ThesametypeofbridgeispresentalsowithintheBorromeansheets(intralayer),leadingtoanarraydenedbytheauthorsas"interlockedBorromeanlayers",whichoverallresultsinasingletrinodalself-catenated3Dnetoftopology3,4,4T93.
ForthisreasonwehavenotincludedFUWVUPinTable2.
Inveryrecenttimes,severalentanglementsbasedonn-Borromeanlinkshavebeenobservedthatexhibitincreasedcomplexity.
Thereisanentireworldtobediscoveredinthefutureofnewintriguingandstimulatingentangledsystemsofthistypethatwillneedsomerationalization.
140Forexample,theexcitingcaseofMUHVOB(andoftheidenticalMUH-VOB01)125representsanimportanttopologicalnovelty,inthatitis,atpresent,theuniqueexampleofa2D5-Borromeanentanglement.
ItconsistsoftheinterweavingofvecoplanarhcblayersjoinedexclusivelyviaBorromeanlinks(theauthorsdescribedthesystemsimplyintermsof2D5-foldinter-penetration).
Similartothemoreusual3-Borromean(3-Brunnian)sheets,allthelayerssharethesameaverageplane,butincontrast,theentanglementisdrasticallymorecomplexandnon-Brunnian.
Intheanalysisofthesecomplexlinks,asomewhathelpfulapproachmaybethecompletecharacterizationoftopologicalpropertiesofthe"basic"or"fundamental"linkthatcomprisesallFigure27.
2DBorromeanentanglementshowingtheBrunnianproperty.
Figure28.
3DBorromeanentanglementobserved(noticethatitisnotBrunnian).
Figure29.
2DBorromeanentanglementofsqlobservedinH-bondedUGUGAF.
Figure30.
Exceptional3DBorromeanpolyrotaxane:grayringsrepresentcucurbiturilmolecules.
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Usingtheconceptsoftheknotsandlinkstheory,wecanfollowthesuggestionsbyLiangandMislow135inordertondacuttingpathwayandtherelevantBrunn'scuttingnumbersμandM.
Theminimumcuttingnumberμisthesmallestnumberofcutsthatsucetounlinkalltheremaininguncutlinks,whilethemaximumcuttingnumberMisthelargestpossiblenumberofcutsthatcanbeappliedtounlinkalltheremaininguncutrings.
Thus,thedistinctionbetweenBorromeanlinkswithandwithouttheBrunnianpropertyisthatμ=M=1fortheformerandM>1forthelatter.
Inthepresentcase(seeFigure32),eliminationofoneringleavesvepossibledierent,allnontrivial4-Borromeanlinks,whileeliminationoftworingsproduces10dierententangle-mentsofwhichvearetrivialandveare3-Borromeanlinks.
Thus,μ=2andM=3.
Theseresultsarereferredtothesingle5-Borromeanfundamentallink.
Obviously,itcomesoutthatifthefundamentallinkisnon-Brunnian,thesameholdsfortheentireentanglement.
Otherextrapolationsfromthefundamentallinktothewholeentanglement,ontheotherhand,arediculttoformulate,andfurtherstudiesonthissubjectaresurelyneeded.
Itseemsalsothatifweremovetwoselectedappropriatelayerswecangetthreeseparatedlayers,sobyanalogyIs=2.
AnevenmorecomplexcaseisthatoftheH-bondedorganicmoleculesinthecocrystal[2TCA·3dpyb][whereTCA=1,3,5-tris(4-carboxyphenyl)adamantaneanddpyb=1,4-di(pyridin-4-yl)benzene](FUYBUX141)thatwemustmentionherebecauseofitsintriguingtopology,thoughitdoesnotbelongtotherealmofcoordinationnetworksobservedinthisreview.
AgainthestructureiscomposedofparallelhoneycomblayersthatareentangledexclusivelyviaBorromeanlinkstogiveanoverall3Dsystem(2D→3D).
Wecanrationalizethearrayasconsistingofstacked7-foldentangledsheets(seeFigure33).
These7-Borromeansheetscontainsevenhcbcoplanarlayers.
Thus,wecaninterestinglycomparethefundamentallinkinthreesituationsofincreasingcomplexitythatcontainthree(any3-Borromean),ve(MUHVOB),andseven(FUYBUX)layersthatsharethesameaverageplanebutshowagrowingnumberoftripletsinvolvedintheentanglement(1,10,and35perfundamentallink,respectively).
AtripletisasystemcomprisingthreeBorromeanlinkedrings;thenumberoftripletscanbeassumedasthenumberofcombinations(viaBorromeanlinks)ofNringstakenthreeatatime.
Moreover,these7-Borromeansheetsareinterlinkedwiththetwoadjacent(upperandlower)sheetsviaotherBorromeanlinks.
Indetail,eachindividuallayerofa7-foldsheetislinkedwithtwoindividualmotifsoftheupperandwithtwoofthelowerentangledsheet,resultinginthiswayinanoverall3Darchitecture.
Thesituationcanbecomparedwiththatofthepreviouslydescribed3DBorromeanspecies(inTable2),withthenotabledierence[2D(7-fold)→3D]insteadof[2D(single)→3D].
3.
6.
MixedTypesofEntanglementof2DMotifsInthislastsection,weexaminethepossiblepresenceofmorethanonetypeofentanglementof2Dmotifs(equalordierentinnature)inthesamecrystalspecies.
Intheprevioussectionswehaveunderlinedthattheentanglementscaninvolve2Dlayersthatdierintopology,composition,orconformationoftheligandsbutthatareentangledinonemanneronly.
Averylimitednumberofcases,however,cannotbeincludedintheabovelistedgroups(illustratedinFigure7)becauseofthecontemporaryFigure31.
Alternated2DBorromeanlayers.
Figure32.
2D5-Borromeannon-Brunnianlayers.
Figure33.
3DBorromeanentanglementof2D7-foldBorromeanintheH-bondedFUYBUX.
Atthetop,asideviewofa7-foldBorromeansheetisillustratedthatrevealsalsotheinterlinkofonemotifofthecentral7-foldsheetwithonemotifoftheadjacentupperandonemotifoftheloweridenticalsheets.
ChemicalReviewsReviewdx.
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org/10.
1021/cr500150m|Chem.
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2014,114,755775807573presenceofdierenttypesofentanglementofthelayers(seeTable3).
Anextremesituationconsistsofthepresenceofbothsingleandinterpenetrated2Dlayerssimultaneously.
Threeofthesespecies(FAGCASandFAGCEW143andVAMXEO01144)showthestackingofalternatesingleand2-foldinterpenetratedlayers.
Interestingly,[Zn(tp)(bphy)](VAMXEO)156wasalsoisolatedwithoutclathratesolventsandconsistsofthesame2-foldlayersasVAMXEO01144butwithoutintercalationofsingleones,thedierencearisingfromtheconditionsandratioofreactantsusedinthesolvothermalsynthesis.
Ontheotherhand,inACUCAC142weobservetwodistinctsinglelayersintercalatingintothestacked2-foldinterpenetratedlayers(seeFigure34).
Otherspecies(XOFYUM157andOWUFOC158)containingpolymeric1Dmotifsintercalatedwithin2-foldinterpenetratedlayershavebeenomittedhereandconsideredonlyfromthepointofviewoftheinterpenetrationphenomenon.
Themostpopulatedgroup(eightentries)consistsofn-foldinterpenetratedlayersthatarefurtherpolycatenatedinaparallelfashiontogivetheoverall3Dstructure(PCATof2-foldor3-foldinterpenetratedlayers).
Hereweobservebothinterpenetrationandparallelpolycatenationof2Dlayers,thatis,twodistincttypesofentanglementinthesamespecies.
159Then-foldinter-penetratedmotifs(2-foldinsixcasesand3-foldintwocases)arecharacterizedbythecoplanarityoftheinvolvedlayers(thatsharethesameaverageplane,asdiscussedabove).
Thesearefurthercatenatedwiththeadjacent(upperandlower)identical(parallelbutoset)interpenetratedmotifstogivethe3Darray.
Theentanglementsherediscussedcontainindividualmotifsthatareeithermarkedlyundulatedsinglelayersorthickdoublelayers.
Itisinterestingtocomparethe2-foldinterpenetratedspecies(seeFigure35).
TherearetwodistinctgroupsdependingTable3.
MixedEntanglementsof2DLayersrefcodecompdformulaatypeofentanglementblayertopology,stackingdirection,nodeyear,ref1ACUCAC[Zn4(peba)8]·(Hpeba)·H2OINT-2f(A)/2D(B)/2D(C)csql,[001],Zn2001,1422FAGCAS[Ag(bpp)2]AsF6INT-2f(A)/2D(B)dsql,[001],Ag2002,1433FAGCEW[Ag(bpp)2]PF6INT-2f(A)/2D(B)dsql,[001],Ag2002,1434VAMXEO01[Zn3(tp)3(bphy)3]·2DMF·10H2OINT-2f(A)/2D(B)dsql,[010],Zn2012,1445ISABUZ[Ag(tcphb)(CF3SO3)]·0.
5H2OPCATofINT-2fehcb,[010],Agandtcphb2004,1456VAJSIK[Zn(nip)(1,4-bpeb)]·2H2OPCATofINT-2fesql,[101],Zn2010,1467WAPCIBCd2(nbpdc)2(1,3-bix)2H2OPCATofINT-2fe3,4L127,[001],Cd2012,1478KAXTUA[Ag6(tipa)4(β-Mo8O26)][H2(β-Mo8O26)]·5H2OPCATofINT-2ff3,3L20,[112],Agandtipa2012,1489MATJIC[Ni5(pda)5(bpp)5]·12H2OPCATofINT-2ffsql,[001],Ni2012,14910OHAYOM[Zn(mfda)(bpp)]PCATofINT-2ffsql,[010],Zn2009,15011XOPLEU[Cd(pyada)2(ClO4)2(CH3CH2OH)2]PCATofINT-3fgsql,[001],Cd2009,15112VUHCUX[Ag3(tppt)2](ClO4)3·8DMSOPCATofINT-3fhhcb,[102],tppt2009,15213CAXVAA[Zn10(bbc)5(bpdc)2(H2O)10]NO3(DEF)28(H2O)8PCAT+INT(hcb)ihcb,3,3,4,5L14,[001];bbc,Zn2(COO)32012,15314PAQCOZ[Ag(cpba)2]SbF6ICATofINT-2fjsql,[110]and[110],Ag1998,15415REBBUX[Zn2(L1)(H2O)]·NO3·DMFICATofINT-2fkhcb,[100]and[010],L1andZn2(COO)32012,155aAbbreviationsforligands:bphy=1,2-bis(4-pyridyl)hydrazine;bpp=4,4′-propane-1,3-diyldipyridine1,3-bis(4-pyridyl)propane;cpba=3-cyanophenyl4-cyanobenzoate;pyada=N,N′-di(4-pyridyl)adipoamide;tcphb=1,3,5-tris(4-cyanophenoxymethyl)-2,4,6-trimethylbenzene;tipa=tris(4-imidazolylphenyl)amine;tppt=2,4,6-tris[4-(pyridin-4-ylthio)methyl]phenyl-1,3,5-triazine;1,3-bix=1,3-bis(imidazol-1-ylmethyl)benzene;1,4-bpeb=1,4-bis[2-(4-pyridyl)ethenyl]benzene;Hpeba=3-[2-(4-pyridyl)ethenyl]benzoicacid;H2bpdc=biphenyl-4,4′-dicarboxylicacid;H2mfda=9,9-dimethyluorene-2,7-dicarboxylicacid;H2nbpdc=2,2′-dinitro-4,4′-biphenyldicarboxylacid;H2nip=5-nitroisophthalicacid;H2pda=phenylenediacrylicacid;H2tp=terephthalicacid;H3bbc=4,4′,4″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate;H3L1=4′,4″,4-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methyleneoxy)]tribiphenyl-4-carboxylicacid;DMF=dimethylformamide;DMSO=dimethylsulfoxide.
bINT-nf=n-foldinterpenetratedcStackingsequenceABCABC.
dStackingsequenceABAB.
eDoc=3(1+1+1);Is=2.
fDoc=5(2+2+1);Is=2.
gDoc=8(3+3+2);Is=3.
hDoc=10(2+2+2+2+2);Is=6.
i2hcb+3,3,4,5L14withDoc=2andIs=1.
jAngle83.
5°,viewdown[001];Doc=3/3.
kAngle90°,viewdown[001];Doc=5/5.
Figure34.
Entanglementswiththepresenceofbothsingleandinterpenetrated2Dlayerssimultaneously.
Figure35.
Parallelpolycatenationof2-foldinterpenetratedlayers.
ChemicalReviewsReviewdx.
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org/10.
1021/cr500150m|Chem.
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2014,114,755775807574onthewayinwhichtheinterpenetratedlayersarestacked,leadingtodierentvaluesofthedegreeofcatenation(Doc).
InhcbISABUZ145andsqlVAJSIK,146alltheundulatedlayersstack,maintainingthesamedirectionoftherunningwaves(stackingnearlyinaAAAAsequence),andthesamehappensforthethicklayer3,4L127inWAPCIB.
147Itturnsoutthateachindividuallayeriscatenatedtoonlyonemotifoftheupper2-foldlayerandoneofthelower2-foldlayerinadditiontothatinterpenetratedinthesameplane(1+1+1),givingDoc=3.
Ontheotherhand,insqlMATJIC,149sqlOHAYOM,150andthethicklayer3,3L20KAXTUA,148uponpassingfromaninterpenetratedlayertotheupperandloweradjacentones,thewaveschangedrasticallytheirrunningdirection(i.
e.
,thestackingsequenceisABAB).
Asaconsequence,eachindividuallayeriscatenatedtoallthemotifsoftheupperandlower2-foldlayersinadditiontothatinterpenetratedinthesameplane(2+2+1),givingDoc=5.
Thetwoexamplesofpolycatenation(XOPLEU151andVUHCUX152)of3-foldinterpenetratedlayersaremorecomplicated.
InXOPLEU,the3-foldinterpenetratedlayersstackinanABABsequence(seeFigure36).
Thisimpliesthateachindividuallayeriscatenatedtoallthreemotifsoftheupperandlowerinterpenetratedlayersinadditiontotwointhesameplane(3+3+2).
Itwascorrectlyobservedthateachsquarewindowofonemotifiscatenatedtosixringsonly:twobelongingtotwomotifsintheupperlayer,twobelongingtotwomotifsinthelowerlayer,andtwointhesameplane.
Nonetheless,thevalueofDocis8,asstatedabove.
Thetwostatements,however,arenotconictingsincethecatenationofonemotifwithanadjacent(upperorlower)motifinvolvesonly2/3oftherings.
InthecaseofVUHCUX,the3-foldinterpenetratedlayersshowadierentstackingwhencomparedwithXOPLEU,thatis,oftheAAAAtype(seeFigure36).
Eachindividualmotifiscatenatedtotwoofthethreemotifsoftheupperandlowerinterpenetratedlayersinadditiontotwointhesameplane.
Moreover,ascorrectlydescribedbytheauthors,the3-foldinterpenetratedlayersareinterlockednotonlywiththetwonearest-neighboringlayersbutalsowiththesecond-nearest-neighboringlayers(seeFigure36).
Therefore,theoverallpolycatenationmotifis(2+2+2+2+2);thatis,theDocvalueis10.
AuniquecaseofmixedentanglementisthatofCAXVAA.
153Inthisspecieswehaveararesimultaneousoccurrenceofbothpolycatenation(involvinghoneycombtriplelayers3,3,4,5L14withDoc=2andIs=1)andinterpenetrationoffourhcblayersforeachofthetripleones,asshowninFigure37.
Thesimultaneousexistenceofinterpenetrationandinclinedpolycatenationisaquiterareevent,andauniquestructurehasbeenknownformanyyearssince1998(PAQCOZ).
154Onlyin2012wasthesecondcasereported(REBBUX).
155Inbothspecies,twosetsof2D2-foldinterpenetratedlayersofsqlandhcbtopology,respectively,areinterlacedinaninclinedfashion.
ThedierenceintheentanglementsconsistsmainlyofthefactthatinPAQCOZeachsquareringiscatenatedwiththreeringsofthreeotherlayers(1+1+1),givingDoc=3/3,whileinREBBUXeachhcbringiscatenatedwithveringsofveotherlayers(1+2+2),givingDoc=5/5(seeFigure38).
Intheformerspeciesaringiscatenatedwithoneinclined2-foldinterpenetratedlayer,whileinthelatterspeciesitiscatenatedwithtwosuchinterpenetratedlayers.
Finally,wemustbrieymentioninthissectionthecaseofAg2[1,2-bis(4-pyridyl)ethane]2(4,4′-biphenyldicarboxylate)(WUJDIO80)thatisincludedinthegroupofparallelFigure36.
Parallelpolycatenationof3-foldinterpenetratedlayers.
Figure37.
Uniqueexampleofparallelpolycatenationofthicklayers(blueandgreen)withinterpenetrationofsinglehcb(red).
ChemicalReviewsReviewdx.
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2014,114,755775807575polycatenatedframeworks.
Itwaspreviouslydiscussedingreatdetailforitsunusualandpuzzlingtopologicalfeatures.
2cThestructureiscomposedoftwodistinctsetsofparallelpolycatenated2Dbilayersof(82.
10)-KIatopologythatappearinextricablyentangled.
However,eachindividual2Dmotifisinterlockedonlybythetwonearest-neighboringonesofthesamesetand,quitesurprisingly,nomotifsofonesetarecatenated(viaHopflinks)byindividualmotifsoftheotherset(seeFigure39).
EachpolycatenatedsethasDoc=2andIs=1,whilethewholearrayhasDoc=2andIs=2.
Theexactnatureofthelinkagebetweenthetwosetsoflayersstillawaitsacorrecttopologicalclassication.
Certainlythecatenationoftheringsofonesetpreventsthedisentanglementoftheothersetandviceversa.
Thesituationisideallycomparabletothatofarecentlyreportedexceptionalspeciesformedbypolycatenationof0Dmetalorganicadamantane-likecages,producinga2-foldinterpene-trated3Dpcunetwork:herethe0Dmotifsarecatenatedonlywithotheronesofthesame3Dnet,buttheircatenationdoesnotallowthedisentanglementoftheentirearchitecture.
2f,1604.
CONCLUSIONSTheinvestigationofentangledtwo-dimensionalframeworkshasshownthatthisisanumerousfamilyincluding783cases(CSD,version5.
34,November2012).
Theentangledphenomenaaccountforabout10%ofthetotal2Dsample,whileinterpenetrationin3Dstructuresaccountsforabout17%.
Inspiteofthisdecrease,thespeciesdiscussedhereareparticularlyintriguingbecauseoftherichnessofthe2Dnettopologyandthevarietyofobservedtypesofentanglement.
Inadditiontothewell-establishedphenomenaofinterpenetration(thedominantone),polycatenation(parallelandinclined),andBorromeanlinkedsystems,otherclassesexhibitingpuzzlingtopologieshavebeenobservedanddiscussed.
Thus,wehaveenvisagedthepossibilityofanewtypeofentanglement,intermediatebetweeninterpenetrationandparallelpolycatena-tion,thatiscomposedofanitenumberoflayerscatenatedinaparallelfashion(n-catenanes),withonlyafewcasespresentlyknown.
Aseparatesectionhasbeendevotedtothedetailedanalysisofentangledlayerscontaining2-nodeloopsthreadedbyedgesofadjacentlayers(43examples).
WithinBorromeanlinkedsystems,inadditiontothewell-knownexamplesofBorromean2DwavesorBorromean3Dframes,wedescribeafewexceptionalcasesofn-foldBorromean(non-Brunnian)layerswithn=5and7.
Wehavealsosystematicallyclassiedforthersttimeallthecasesexhibitingdierenttypesofentanglementinthesamestructure.
Finally,fromthepointofviewofpropertiesandpotentialapplications,theseentangled2Dmotifsshowbehaviorthatcanbeessentiallyconsideredtypicalofdynamic/exibleporousframeworks(softporousmaterials)thatcanrespondtoexternalstimuliofvarioustypesbychangingtheirporosity.
Thisleadstoguest-inducedtransformations,solid-statereactions,breathingbehavior,selectivemolecularrecognition,anddierentmagneticproperties.
Interestingly,ofthedierenttypesofentanglement,polycatenatedspecies(parallelandinclined)seemthemorepromising.
Thoughsomeoftheseraretypesofentanglementmaynowappearsomewhatexotic,webelievethatotherexamplesofsuchunusualsystemswillbeobservedinthenearfutureandthatarationalizationoftheircomplexitycanbeausefulcontributiontotheengineeringofcoordinationpolymersandmetalorganicframeworksandtheirproperties,consideringtheexplosivegrowthofthisareainrecentyears.
ASSOCIATEDCONTENT*SSupportingInformationReferencesandclassicationforall783structuresexamined(xls);onetable,listingthedistributionofnetworktopologiesamongPCATentanglement,andthreegures,showing17thicklayersalreadyobservednonentangled,VUKHEPintwopossiblerepresentations,andasinglekgdobservedin2-foldinter-penetratedTONFUY(pdf).
ThismaterialisavailablefreeofchargeviatheInternetathttp://pubs.
acs.
org.
AUTHORINFORMATIONCorrespondingAuthors*E-maillucia.
carlucci@unimi.
it.
*E-maildavide.
proserpio@unimi.
it.
*E-mailblatov@samsu.
ru.
NotesTheauthorsdeclarenocompetingnancialinterest.
Figure38.
Inclinedpolycatenationof2-foldinterpenetratedhcblayers.
Ontherightthecatenationofone6-ring(inred)withveringsfromvedierentlayersshowstheoriginofDoc5/5from5=2+2+1.
Figure39.
ParallelpolycatenationoftwosetsofKIalayersobservedinWUJDIO.
ChemicalReviewsReviewdx.
doi.
org/10.
1021/cr500150m|Chem.
Rev.
2014,114,755775807576BiographiesLuciaCarlucciwasborninItalyin1963.
Sheobtainedthe"Laurea"degreeinIndustrialChemistry(1989)andaPh.
D.
inChemicalSciences(1993)fromtheUniversityofBologna.
ShemovedtotheUniversityofMilanin1993.
Since2010shehasbeenAssociateProfessorofGeneralandInorganicChemistryattheDepartmentofChemistryofthesameuniversity.
Afterearlyinterestsinorganometallicchemistry,herresearchactivitywasorientedtoporouscoordinationpolymersandfocusedonthedevelopmentofnewdesignedligandsandsyntheticstrategies,X-raydiraction,andtopologicalandentanglementanalyses.
GianfrancoCianiwasborninFerrara(Italy)in1944.
Heretiredfromacademicactivityin2010afterbeingFullProfessorofInorganicChemistryattheUniversityofMilanoandDirectorofDCSSI.
Since1969inMilano,hisactivitywasdevotedtoX-raycrystallographicstudiesofcoordinationandorganometalliccompounds,mainlycarbonylmetalclusters.
Since1993hismaininteresthasbeendevotedtothestudyofcoordinationnetworksandtheirtopologiesandtothecrystalengineeringofmineralomimeticandnanoporous2Dand3Dnetworks.
Heistheauthorofover236publications.
DavideM.
ProserpiowasborninItalyin1962.
In1986heearnedthe"'Laurea'"degreeinChemistryattheUniversityofPavia.
InthenextveyearshewasactiveintheeldofappliedtheoreticalchemistryunderthesupervisionofCarloMealli(CNR,Florence,Italy)andRoaldHomann(CornellUniversity,Ithaca,NY).
Since1991hehasbeenattheUniversityofMilano,asanAssociateProfessorfrom2003,withspecialinterestintopologicalcrystalchemistry:interpenetration,polycatena-tion,andpolythreadingofnets.
TatyanaG.
Mitinawasbornin1988inMednogorsk,Orenburgregion,Russia.
ShegraduatedfromSamaraStateUniversityin2010andnowisaresearcheratSamaraCenterforTheoreticalMaterialsScience.
Herresearchinterestsconcerntopologicalanalysisoftwo-periodiccoordinationpolymersandapplicationsofcomputermethodstothedesignofnewmaterials.
VladislavA.
Blatovwasbornin1965inSamara(formerlyKuibyshev),Russia.
HegraduatedfromSamaraStateUniversity(1987)andearneddegreesofCandidate(1991)andDoctorinChemistry(1998)fromtheInstituteofGeneralandInorganicChemistry(Moscow).
HehasbeenaFullProfessorintheSSUChemistryDepartmentsince1998andChemicalReviewsReviewdx.
doi.
org/10.
1021/cr500150m|Chem.
Rev.
2014,114,755775807577directoroftheSamaraCenterforTheoreticalMaterialsSciencesince2013.
HisresearchandeducationalinterestsconcerngeometricalandtopologicalmethodsincrystalchemistryandtheircomputerimplementationintheprogrampackageTOPOS,beingdevelopedsince1989.
ACKNOWLEDGMENTSD.
M.
P.
,T.
G.
M.
,andV.
A.
B.
thanktheRussiangovernment(Grant14.
B25.
31.
0005)andtheRussianFoundationforBasicResearch(Grant13-07-00001)forsupport.
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