SupramolecularChemistry:

GeneralPrinciples,SelectedExamplesandApplications

YanhuaLan

Contents
HistoricalNotes KeywordsandDefinitions DifferentTypesofSupramolecular Interactions DisciplineofSelfassembly Examples: Grids,fromLigand DesigntoSelfassemblyProcess Application
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Inthe1990s,supramolecularchemistrybecameevenmore sophisticated,withresearcherssuchasJamesFraserStoddart developingmolecularmachinery andhighlycomplexself assembled structures,andItamarWillnerdevelopingsensorsand methodsofelectronicandbiologicalinterfacing.Duringthis period,electrochemical andphotochemical motifsbecame integratedintosupramolecularsystemsinordertoincrease functionality,researchintosyntheticselfreplicatingsystem began,andworkonmolecularinformationprocessingdevices began.Theemergingscienceofnanotechnology alsohada stronginfluenceonthesubject,withbuildingblockssuchas fullerenes,nanoparticles,anddendrimers becominginvolvedin syntheticsystems.

Keywords
Supramolecular chemistry thechemistrybeyondthemolecule orthechemistryofthe noncovalent bond (Lehn 1988,1994,1995). themolecularcomponentsareheldtogetherandorganisedby meansofnoncovalentbindinginteractions. Metallosupramolecular chemistry Themetalsactasatypeofglue toholdtogetherassemblies oforganicmolecules atermintroducedbyConstablein1994. Byemployingdonorgroupsinorganicmolecules(ligands)that bridgemorethanonemetalcentreitispossibletoconstruct one,two orthreedimensionalarchitectures,basedonML 7 interactions.

MolecularRecognition
Molecularrecognitionisthespecificinteractionbetweentwo

molecules,whicharecomplementaryintheirgeometricand electronicfeatures(liketwofittingpiecesofajigsawpuzzle).
Theclassicallockandkeyprincipledescribestheinteractionof

componentsduetotheirshapeandrigidity(preorganization).

Selfassembly
Recognitionbetweenmoleculesleadstoanaggregation,which

finallyresultsinanensemblethatiscomposedoftwoormore discreteunits(Philp andStoddart 1996;Lawrenceetal.1995).

mixingofthecomponentsspontaneouslyaffordsonlyonewell

definedproduct.
Strictselfassembly:directlyproceedstowardtheformationofawell

definedaggregate. Directed(templated)selfassembly:controlled/influencedbysome additionalspecies,e.g.,templates(Lindsey1991).Thismeans,inan idealizedcaseselfassemblyfollowsacooperative orallostericprocess. 8 thermodynamicallymoststablespecies.

Supermoleculesvs.SupramoleularAssemblies
Supermolecules welldefined,discretespeciesformed fromadefined,finitenumberof molecules theequivalentoflowmolecularweight organicmolecules hostguestchemistry SupermolecularAssemblies polymolecularentitiesfrom spontaneous,butdefinedassociationof manymolecules theequivalentofhighmolecular weightpolymersandmacromolecules supramolecularselfassembly

individualnoncovalentinteractionsmaybeweak,but manyofthemwillstillyieldstable structureswhile allowingforselfhealing (errorcorrection).

J.M.Lehn,PureAppl.Chem.1978,50,871. G.M.Whitesides,Science2002,295,2418; Proc.Natl.Acad.Sci.USA2002,99,4769

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Supramolecularinteractions(Noncovalentinteractions)mightbe roughlyclassifiedinthefollowingcategories:

MarkusAlbrecht,Naturwissenschaften,2007,94:951966. JonathanW.Steed,DavidR.Turner,KarlJ.Wallace,CoreConceptsin SupramolecularChemistryandNanochemistry,JohnWiley&Sons,Ltd,2007

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 IonIonInteractions:
Strong(200300KJ/mol) Ionion interactionsarenondirectionalinnature,meaning thattheinteractioncanoccurinanyorientation.

Tetrabutylammoniumchloride

Forexample:Acidbasepairsinparticularinproteins
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 IonDipoleInteractions:
Moderatelystrong(50200KJ/mol); Strongerwhenpartiallycovalent(100400KJ/mol)

sodiumcomplexofcrown5

Cation bindinghosts

metalcomplexes(partiallycovalent)
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DipoleDipoleInteractions
Relativelyweak(550KJ/mol) Despitebeingtheweakestdirectionalinteraction,dipoledipole interactionsare usefulforbringingspeciesintoalignment,astheinteractionrequiresaspecific orientationofbothentities.

dipoledipoleinteractionsinacetone;dipolemoment2.91D

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Electrostaticinteractionsarecausedbytheattraction(Coulombic) betweenoppositecharges/differentlychargedionsordipoles.
Ionion interactionsarenondirectionalinnature,meaning thattheinteractioncanoccurinanyorientation. Iondipoleanddipoledipoleinteractions,however,have orientationdependantaspectsrequiringtwoentitiestobe alignedsuchthattheinteractionsareintheoptimaldirection.

Electrostaticinteractionsplayanimportantroleinunderstandingthefactors thatinfluencehighbindingaffinities,particularlyinbiologicalsystemsin whichthereisalargenumberofrecognitionprocessesthatinvolvecharge charge interactions;indeedtheseareoftenthefirstinteractionsbetweena substrateandanenzyme.

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 Hydrogenbonding(I)
Hydrogenbonddonorsaregroupswithahydrogenatom attachedtoan electronegative atom(suchasnitrogenoroxygen),thereforeformingadipole withthehydrogenatomcarryingasmallpositivecharge. Hydrogenbondacceptorsaredipoleswithelectronwithdrawing atomsbywhich thepositivelychargehydrogenatomcaninteract,forexample,carbonylmoieties.

Acarbonylacceptingahydrogenbondfromasecondaryaminedonor(a)and(b)the standardwayofexpressingdonorandacceptoratoms(D,donoratom;A,acceptoratom).
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 Hydrogenbonding(II)

Varioustypesofhydrogenbondinggeometries:(a)linear;(b)bent;(c) donatingbifurcated;(d)acceptingbifurcated;(e)trifurcated;(f)three centrebifurcated.

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 Hydrogenbonding(III)
themostimportantnoncovalentinteractioninthedesignofsupramolecular architectures,becauseofitsstrengthandhighdegreeofdirectionality.It representsaspecialkindofdipoledipole interactionbetweenaprotondonor (D)andaprotonacceptor(A).

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MultipleHydrogenBondingSitesinDNABasePairs
complementaryarrangementsofhydrogenbondacceptors/donorsforselective binding mutuallyenforcingdonorsandacceptors

(a) Primaryandsecondaryhydrogenbondinteractions betweenguanineandcytosinebasepairsinDNA (b) Andaschematicrepresentation.

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21

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 . Interactions
(i) cation interactions relativelyweak(580KJ/mol)

alkaline andalkalineearthmetalsalsoforminteractionswithdoublebond systems.Forexample,theinteractionofpotassiumionswithbenzenehasa similarenergytotheK+ OH2 interaction. bis(benzene)chromium covalent(nocharges) ferrocene mainlycovalent
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and(ii) interactions
Weak(550KJ/mol)

Thetwotypesof interactions: (a)facetoface;(b)edgetoface.

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(a) Top and (b) side views of the layered structure of graphite, held together by face-to-face -interactions.

Thelayeredstructureofgraphiteisheldtogetherbyweak,faceto faceinteractionsandthereforefeelsslippery.Itisbecauseofthe slippagebetweenlayersthatgraphitecanbeusedasalubricant (albeitinthepresenceofoxygen). Interactionsinvolvingsystemscanbefoundinnature,forexample,the weakfacetofaceinteractionsbetweenbasepairsalongthelengthofthe doublehelixareresponsiblefortheshapeofDNA.

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vanderWaalsinteractions (mutuallyinduceddipoles)
Weak(220KJ/mol) Dispersioneffects:Londoninteractionandtheexchangeandrepulsion interaction vander Waals interactionsarisefromfluctuationsoftheelectron distributionbetweenspeciesthatareincloseproximitytooneanother.

ALondoninteractionbetweentwoargonatoms.Theshift oftheelectroncloudaroundthenucleusproduces instantaneousdipolesthatattracteachother

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 vanderWaalsinteractions

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 Hydrophobiceffects
Hydrophobiceffectsarisefromtheexclusionofnonpolargroupsor moleculesfromaqueoussolution.Thissituationismoreenergetically favourable becausewatermoleculesinteractwiththemselvesorwith otherpolargroupsormoleculespreferentially.

Twoorganicmoleculescreatingaholewithinanaqueous phase,givingrisetotheentropichydrophobiceffect oneholeismorestablethantwo.

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 Hydrophobiceffects
enthalpic hydrophobiceffect

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Projectionofachainwithinthestructureof[Ni2(cischdc)2(dpa)2] showingthe overlapofthepyridine indpa andthehydrogenbonds (dotted)betweenHofdpa (di2pyridylamine) andOofcischdc (1,4cyclohexanedicarboxylate)

Kumagai,CrystalGrowth&Design,9(6),2009,27342741.
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MultivalencyandCooperativity

Multivalency isthebindingoftwoormoreentitiesthatinvolvesthesimultaneous interactionbetweenmultiple,complementaryfunctionalitiesontheseentities. Thefactthattheresultingbindingconstant(i.e.,bindingenergy)isoftenhigher thanexpectedfromitsindividualcomponentsisknownascooperativity.

A.Mulder,J.Huskens,D.N.Reinhoudt,Org.Biomol.Chem.2004,2,3409

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DisciplineofSelfassembly

Twocommontypesofbuildingblocksfor perpendicularcoordinationarrangements

bidentate binding pocket

tetrahedral metal ion

terdentate binding pocket

octahedral metal ion

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SelfassemledArchitectures:
Ladders,Lattices,Polygons,Grids,Helicates,Rotaxanes,Catenanes, Knots,Cages,Cubes,Capsules

Trinucleardoublehelicate

M.Fujita, P.Stang, J.Lehn, J.P,Sauvage, E.Constable

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Ligand design
Diazines asbridgingligands

6
N N

6 N

4 N

6 N 2 5 N 3

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- Grids
Gridsinvolveasetofparallelligand components heldmoreorlessorthogonallytoanothersetof parallelligand componentswithmetalionsat thecrossingpoints.

+ 4

[2 x 2]

+ 9

[3 x 3]

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 Pyridazinecontaininggrids
Bisbidentate ligand
[CuI4(I)4](CF3SO3)4

N N I

Youinou M.T.,Rahmouni N.,FischerJ.,OsbornJ.A.,Angew.Chem.Int.Ed. Engl.,1992,31,733.

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8+
N N N
M

4+
H N N
M

NH NH N M N Ph

NH NH N

H N N Ph N N Ph N
M

N Ph

Ph N

N NH NH N

N
N H

N H

N N

NH
M

NH N Ph

Y.Lan,PhDthesis,UniversityofOtago,Dunedin,NewZealand

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Selfassemblyoftetranuclear [2x2]gridcomplexesof(L7)2 (metal:ligand:base =4:4:8)

0
N

N
NH

N N N

O N N N Ph

NO N

4
O

Ph
N

(BF4)2.xH2O 8 TEA

Ph
O

Ph

NH

N O

N N N N

NO
N

N N N Ph O N

H2L7

= M (Zn, Cu, Ni, Co)

[ZnII4(L7)4]3H2O [CuII4(L7)4]3H2O [NiII4(L7)4]6H2O [Co4(L7)4](BF4)0.2511H2O2CH3OH

Y.Lan,PhDthesis,UniversityofOtago,Dunedin,NewZealand
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[CoII4(III)4](BF4)8

Bisterdentate ligand
N
N

H N

H N

N
N

III

RubenM.,Lehn,J.M.,VaughanG.,Chem.Commun.,2003,1338.

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MolecularSwitch
Electrochemicalpropertiesof[CoII4(II)4](BF4)8
N N N Ph II N N N

Tenwellresolvedreversible reductionstepsinvolving elevenelectronsat20oC; Thefirstexampleofthe highestreportednumberof electrontransferstepsfora molecularcompound.

RubenM.,Breuning E.,Gisselbrecht J.P.,Lehn J.M.,Angew.Chem.Int. Ed.,2000,39,4139.
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Opticalpropertiesof[CoII4(III)4](BF4)8

Opticalswitching,with intensereversiblecolour changes(paleyellowat lowpHtoorangeand finallydeepvioletabove neutralpH). ColourchangeatdifferentpH

RubenM.,Lehn J.M.,VaughanG.,Chem.Commun.,2003,1338.
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Gas,SolventStorages;GasSeparation
TheunsaturatedCu2+siteswereobserved tobindD2 atincreasedD2 loading CrystalstructureofCu3(btc)2andthe positionoftheCu2+boundD2 molecules (yellowspheres)asdeterminedbypowder neutrondiffraction.Green,red,andgray spheresrepresentCu,O,andCatoms, respectively. Infraredstretchingbandat4100cm1, characteristicofmetalH2 interactions. ZerocoverageH2 bindingenthalpyis increased. H2 adsorptioncapacityshowsH2 uptake.
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J.Long,Angew.Chem.Int.Ed.2008,47,6766 6779; Batten,Angew.Chem.Int.Ed.2009,48,89198922

Supramolecularmagneticmaterials:
{CuLn} unit: Ln = Tb

a)
right - . left-

3 {CuLn} units linked through trimesic acid: Ln = Dy

b)

d)

Right- and lefthanded propellers interweave to give the full [{CuDy}3]2 motif

The 3-bladed propeller motif of {CuDy}3

c)

e)
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Supramolecular DoublePropeller Dimers ofHexanuclear CuII/LnIII Complexes:A{Cu3Dy3}2 SingleMolecule Magnet,G.Novitchi,W.Wernsdorfer,L.F.Chibotaru,J.P.Costes,C.E.Anson,A.K.Powell,Angew.Chem.

Magnetic behaviour for {CuDy} and [{CuDy}3]2

Hysteresis for {CuDy} (field dependence at different frequencies).

M/Ms

What is the origin of the dramatic enhancement of SMM properties in forming the dodecanuclear supramolecular complex? Hysteresis for [{CuDy}3]2 (field dependence at different frequencies).

M/Ms

Answer seems to lie with the imposed arrangement of the Dy centres.

Bulk susceptibility studies show very small Cu-Dy coupling, as expected.

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GuestTunableStructureandSpinCrossoverProperties

SCOF2is[Fe(NCS)2(bpbd)2]andbpbd is2,3bis(4pyridyl)2,3butanediol (a) InterpenetratinggridstructureofSCOF2(guest) (b)square1Dporeswhereguestmoleculesreside. C.J.Kepert,J.AM.CHEM.SOC. 2009,131,1210612108

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C.J.Kepert,J.AM.CHEM.SOC. 2009,131,1210612108

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(SCOF2(Acn)(red),SCOF2(Ac)(orange))andtheprotic (SCOF2(Me)(blue),SCOF 2(Et)(purple),SCOF2(Pr)(green),whereguest)=acetonitrile (Acn),acetone(Ac), methanol(Me),ethanol(Et),and1propanol(Pr). C.J.Kepert,J.AM.CHEM.SOC. 2009,131,1210612108

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