Rapid self-healing and anion selectivity in metallosupramolecular gels assisted by fluorine-fluorine interactions

Article abstract of DOI:10.1039/c7dt00983f

Simple ML₂ [M = Fe(II), Co(II), Ni(II)] complexes obtained from a perfluoroalkylamide derivative of 4-aminophenyl-2,2′,6,2′-terpyridine spontaneously, yet anion selectively, self-assemble into gels, which manifest an unprecedented rapid gel strength recovery, viz. self-healing, and thermal rearrangement in aqueous dimethyl sulfoxide. The key factor for gelation and rheological properties emerges from the fluorine-fluorine interactions between the perfluorinated chains, as the corresponding hydrocarbon derivative did not form metallogels. The perfluoro-terpyridine ligand alone formed single crystals, while its Fe(II), Co(II) or Ni(II) complexes underwent rapid gelation leading to highly entangled fibrillar networks visualized by electron microscopy. The thermodynamic parameters of gelation based on variable temperature NMR ¹H and ¹⁹F resonances showed that gelation was enthalpically favourable and entropically disfavourable. The step strain rheological experiments revealed that the gels undergo rapid self-healing and the morphological features, thermal stability and mechanical properties were found to depend on the nature of the metal ion.

Full text of DOI:10.1039/c7dt00983f

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Sanchez, N. Nonappa, S. Bhowmik, S. Hietala, R. Puttreddy, M. Lahtinen, L. De Cola and K. Rissanen,
Dalton Trans., 2017, DOI: 10.1039/C7DT00983F.
Volume 45 Number
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January 2016 Pages 1–398
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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
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DOI: 10.1039/C7DT00983F
JournalꢀNameꢀ
ꢀ
ARTICLEꢀ
RapidꢀSelf-HealingꢀandꢀAnionꢀSelectivityꢀinꢀMetallosupramolecularꢀ
GelsꢀAssistedꢀbyꢀFluorine-FluorineꢀInteractionsꢀ
arnReceivedꢀ00thꢀJanuaryꢀ20xx,ꢀ
Acceptedꢀ00thꢀJanuaryꢀ20xxꢀ
a
b
a
c
a
LeticiaꢀArnedo-Sánchez, ꢀNonappa, ꢀSandipꢀBhowmik, ꢀSamiꢀHietala, ꢀRakeshꢀPuttreddy, ꢀManuꢀ
a ꢀ
d
a*ꢀ
Lahtinen , LuisaꢀDeꢀCola ꢀandꢀKariꢀRissanen
DOI:ꢀ10.1039/x0xx00000xꢀ
2
SimpleꢀML ꢀ[M=ꢀFe(II),ꢀCo(II),ꢀNi(II)]ꢀcomplexesꢀobtainedꢀfromꢀaꢀperfluoroalkylamideꢀderivativeꢀofꢀ4-aminophenyl-2,2´,6,2´-
www.rsc.org/ꢀ
terpyridineꢀ spontaneously,ꢀ yetꢀ anionꢀ selectively,ꢀ self-assembleꢀ intoꢀ gels,ꢀ whichꢀ manifestꢀ anꢀ unpresetendedꢀ rapidꢀ gelꢀ
strengthꢀ recovery,ꢀ viz.ꢀ self-healing,ꢀ andꢀ thermalꢀ rearrangementꢀ inꢀ aqueousꢀ dimethylꢀ sulfoxide.ꢀ Theꢀ keyꢀ factorꢀ forꢀ theꢀ
gelationꢀandꢀtheꢀrheologicalꢀpropertiesꢀemergeꢀfromꢀtheꢀfluorineꢀ-ꢀfluorineꢀinteractionsꢀbetweenꢀtheꢀperfluorinatedꢀchains,ꢀ
asꢀ theꢀ correspondingꢀ hydrocarbonꢀ derivativeꢀ didꢀ notꢀ fromꢀ metallogels.ꢀ Theꢀ perfluoro-terpyridineꢀ ligandꢀ aloneꢀ formedꢀ
singleꢀ crystals,ꢀ whileꢀ itsꢀ Fe(II),ꢀ Co(II)ꢀ orꢀ Ni(II)ꢀ complexesꢀ underwentꢀ rapidꢀ gelationꢀ leadingꢀ toꢀ highlyꢀ entangledꢀ fibrillarꢀ
networksꢀvisualizedꢀbyꢀelectronꢀmicroscopy.ꢀTheꢀthermodynamicꢀparametersꢀofꢀgelationꢀbasedꢀonꢀvariableꢀtemperatureꢀ
1
19
NMRꢀonꢀ Hꢀandꢀ Fꢀresonancesꢀshowedꢀthatꢀgelationꢀwasꢀenthalpicallyꢀfavourableꢀandꢀentropicallyꢀdisfavourable.ꢀTheꢀstepꢀ
strainꢀrheologicalꢀexperimentsꢀrevealedꢀthatꢀtheꢀgelsꢀundergoꢀrapidꢀself-healingꢀandꢀtheꢀmorphologicalꢀfeatures,ꢀthermalꢀ
stabilityꢀandꢀmechanicalꢀpropertiesꢀwereꢀfoundꢀtoꢀdependꢀonꢀtheꢀnatureꢀofꢀtheꢀmetalꢀion.ꢀ
massꢀ organo-ꢀ andꢀ hydrogelatorsꢀ withꢀ newꢀ functionalꢀ
7-20ꢀ
properties.
1
21
22
23
Peptides, ꢀ carbohydrates, ꢀ steroids, ꢀ urea-
Introductionꢀ
2
4
25
derivatives, ꢀ andꢀ simpleꢀ fattyꢀ acids, ꢀ haveꢀ beenꢀ shownꢀ toꢀ
exhibitꢀ remarkableꢀ abilityꢀ toꢀ self-assembleꢀ intoꢀ highlyꢀ
-5 entangledꢀ fibrillarꢀ networksꢀ therebyꢀ ableꢀ toꢀ encapsulateꢀ andꢀ
Metallosupramolecularꢀself-assemblyꢀhasꢀcontinuedꢀtoꢀgainꢀaꢀ
newꢀdimensionꢀdueꢀtoꢀitsꢀabilityꢀtoꢀcontrolꢀtheꢀshapeꢀandꢀsizeꢀ
1
ofꢀ molecular,ꢀ asꢀ wellꢀ as,ꢀ supramolecularꢀ superstructures.
ꢀ
6
Examplesꢀ includeꢀ self-assemblyꢀ intoꢀ cages, ꢀ cubes, ꢀ spheres, ꢀ
7
8
immobilizeꢀsolventꢀmolecules.ꢀWhileꢀaꢀmajorityꢀofꢀtheꢀgelatorsꢀ
2
6,27
9
10
11
haveꢀ beenꢀ discoveredꢀ serendipitously,
ꢀ continuingꢀ effortsꢀ
grids, ꢀ helicates, ꢀ andꢀ metalꢀ organicꢀ frameworks. ꢀ Inꢀ
addition,ꢀtheꢀaboveꢀexamplesꢀalsoꢀprovideꢀdynamicꢀcontrolꢀforꢀ
haveꢀ beenꢀ madeꢀ towardsꢀ rationalꢀ designꢀ ofꢀ gelatorsꢀ withꢀ
tunableꢀ propertiesꢀ asꢀ forꢀ exampleꢀ thermotropicꢀ
1
host-guestꢀ chemistry, ꢀ size-selectiveꢀ entrapment, ꢀ stereo-
2
13
2
polymorphism ꢀ orꢀ stimuli-responsiveness ꢀ includingꢀ anionꢀ
8
29
1
controlledꢀ chemicalꢀ reactions, ꢀ andꢀ supramolecularꢀ
4
3
dependentꢀ gels ꢀ withꢀ interestingꢀ applicationsꢀ inꢀ molecularꢀ
0
1
5
polymers. ꢀRecentlyꢀtheꢀself-assemblyꢀprocessꢀofꢀluminescentꢀ
platinumꢀcomplexesꢀhasꢀbeenꢀvisualizedꢀandꢀcontrolledꢀusingꢀ
theꢀchangeꢀinꢀtheꢀphotophysicalꢀpropertiesꢀofꢀtheꢀcompoundsꢀ
3
1
sensing. ꢀRecently,ꢀmetalꢀcoordinationꢀinducedꢀself-assemblyꢀ
ofꢀ smallꢀ moleculesꢀ leadingꢀ toꢀ solventꢀ immobilizationꢀ andꢀ
gelationꢀhasꢀemergedꢀasꢀaꢀfascinatingꢀareaꢀofꢀresearchꢀinꢀtheꢀ
1
6
uponꢀ aggregation. ꢀ Supramolecularꢀ gelationꢀ onꢀ theꢀ otherꢀ
hand,ꢀ isꢀ continuouslyꢀ evolvingꢀ areaꢀ ofꢀ researchꢀ withꢀ newꢀ
insightsꢀ andꢀ novelꢀ applicationꢀ potentials.ꢀ Non-covalentꢀ
3
2,33ꢀ
fieldꢀ ofꢀ supramolecularꢀ gels.
Inꢀ orderꢀ toꢀ promoteꢀ
supplementaryꢀ interactionsꢀ andꢀ achieveꢀ supramolecularꢀ
gelation,ꢀ moreꢀ thanꢀ oneꢀ non-covalentꢀ interactionꢀ isꢀ needed,ꢀ
therebyꢀfacilitatingꢀself-assemblyꢀatꢀmultipleꢀlengthꢀscales.ꢀAsꢀaꢀ
result,ꢀ additionalꢀ interactionꢀ motifsꢀ suchꢀ asꢀ peptideꢀ bonds,ꢀ
urea-linkersꢀ orꢀ steroidalꢀ unitsꢀ haveꢀ beenꢀ appendedꢀ toꢀ theꢀ
basicꢀ ligandꢀ units.ꢀ Moreover,ꢀ itꢀ hasꢀ beenꢀ shownꢀ thatꢀ byꢀ
combiningꢀ theꢀ metal-ligandꢀ coordinationꢀ bonds,ꢀ alongꢀ withꢀ
additionalꢀ supramolecularꢀ interactionsꢀ andꢀ ligandꢀ design,ꢀ theꢀ
conceptꢀ ofꢀ subcomponentꢀ self-assemblyꢀ canꢀ beꢀ usedꢀ inꢀ
interactionsꢀ suchꢀ asꢀ hydrogenꢀ bonding,ꢀ p-pꢀ stacking,ꢀ chargeꢀ
transferꢀ interactions,ꢀ andꢀ hydrophobicꢀ effectsꢀ haveꢀ beenꢀ
extensivelyꢀ utilizedꢀ towardsꢀ rationalꢀ designꢀ ofꢀ lowꢀ molecularꢀ
a.
NanoscienceꢀCenter,ꢀDepartmentꢀofꢀChemistry,ꢀUniversityꢀofꢀJyväskylä,ꢀP.O.ꢀBox.ꢀ
5,ꢀJyväskylä,ꢀFI-40014,ꢀFinland.ꢀE-mail.ꢀkari.t.rissanen@jyu.fiꢀ
MolecularꢀMaterialsꢀGroup,ꢀDepartmentꢀofꢀAppliedꢀPhysics,ꢀAaltoꢀUniversityꢀ
SchoolꢀofꢀScience,ꢀPuumiehenjuaꢀ2,ꢀEspoo,ꢀFI-02150,ꢀFinland.ꢀ
LaboratoryꢀofꢀPolymerꢀChemistry,ꢀDepartmentꢀofꢀChemistry,ꢀUniversityꢀofꢀHelsinki,ꢀ
P.O.ꢀBoxꢀ55,ꢀFI-00014,ꢀHelsinki.ꢀ
3
b.
c.
34
molecularꢀ gelation. ꢀ Amongꢀ severalꢀ ligandsꢀ studiedꢀ forꢀ
d.
ISIS,ꢀUniversitéꢀdeꢀStrasbourgꢀandꢀCNRSꢀUMRꢀ7006,ꢀ8ꢀrueꢀGaspardꢀMonge,ꢀ
Strasbourgꢀ67000,ꢀFranceꢀ
gelation,ꢀ terpyridineꢀ andꢀ itsꢀ derivativesꢀ wereꢀ shownꢀ toꢀ beꢀ
attractiveꢀ candidatesꢀ becauseꢀ ofꢀ theirꢀ easyꢀ synthesisꢀ andꢀ
functionalizationꢀ asꢀ wellꢀ asꢀ forꢀ theirꢀ abilityꢀ toꢀ bindꢀ aꢀ diverseꢀ
ꢀ
†
ꢀElectronicꢀSupplementaryꢀInformationꢀ(ESI)ꢀavailable:ꢀTheꢀdetailsꢀofꢀSynthesisꢀ
1 13 19
3
5,36
numberꢀ ofꢀ metalꢀ ions.
ꢀ Onꢀ theꢀ otherꢀ hand,ꢀ lessꢀ studiedꢀ
andꢀpurificationꢀofꢀligandsꢀ3,ꢀ3Hꢀandꢀ4,ꢀ H,ꢀ Cꢀandꢀ FꢀNMRꢀspectra,ꢀFT-IRꢀspectra,ꢀ
Singleꢀcrystalꢀdataꢀofꢀligandꢀ3,ꢀitsꢀsolvatesꢀandꢀcomplexꢀ[Ni4 ]Cl2ꢀ(CCDCꢀ1533110-
533114,,ꢀPowderꢀX-rayꢀdiffractionꢀpatternsꢀofꢀsolidsꢀandꢀxerogels,ꢀareꢀavailable.ꢀ
SeeꢀDOI:ꢀ10.1039/x0xx00000xꢀ
2
interactionsꢀ suchꢀ asꢀ halogenꢀ bondingꢀ haveꢀ beenꢀ reportedꢀ toꢀ
3
controlꢀtheꢀself-assemblyꢀofꢀaꢀvarietyꢀofꢀmotifsꢀsuchꢀasꢀureas ꢀ
7
1
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ1ꢀꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ple aDs ea ꢀl dt oo nꢀ n To rt aꢀ and sj ua sc tt ꢀimo na sr ginsꢀ
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ARTICLEꢀ
JournalꢀNameꢀ
3
andꢀ peptides ꢀ leadingꢀ toꢀ hydrogelation.ꢀ Weakꢀ interactionsꢀ Theꢀ startingꢀ materialꢀ 4-aminophenyl-2,2´:6´,2´´-terpyridineꢀ 2ꢀ
8
View Article Online
DOI: 10.1039/C7DT00983F
includingꢀfluorineꢀ-ꢀfluorineꢀ(F···F)ꢀinteractions,ꢀareꢀalsoꢀgainingꢀ wasꢀ synthesizedꢀ accordingꢀ toꢀ theꢀ literatureꢀ procedureꢀ
5
7
attentionꢀ inꢀ theꢀ fieldꢀ ofꢀ contemporaryꢀ supramolecularꢀ reportedꢀ previously. ꢀ Theꢀ gelatingꢀ ligandꢀ N-(4-([2,2':6',2''-
3
9-43
44
chemistry.
pharmaceuticallyꢀ importantꢀ molecules
extensivelyꢀ studied.ꢀ Beyondꢀ beingꢀ aꢀ consequenceꢀ ofꢀ crystalꢀ ofꢀ pentadecafluorooctanoylꢀ chlorideꢀ
ꢀPreviously,ꢀfluorinatedꢀsolventsꢀ(fluorous) ꢀandꢀ terpyridin]-4'-yl)phenyl)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-penta-
4
5,46
ꢀ
haveꢀ beenꢀ decafluorooctan-amideꢀ
3
ꢀ wasꢀ preparedꢀ byꢀ dropwiseꢀ additionꢀ
toꢀ aꢀ solutionꢀ ofꢀ ꢀ inꢀ
1
,
ꢀ
2
packing,ꢀ recentꢀ experimentalꢀ andꢀ theoreticalꢀ studiesꢀ haveꢀ anhydrousꢀ dichloromethaneꢀ andꢀ inꢀ theꢀ presenceꢀ ofꢀ N,N-
supportedꢀ theꢀ existenceꢀ ofꢀ F···Fꢀ interactionsꢀ andꢀ openedꢀ upꢀ diisopropylethylꢀamineꢀ(Fig.ꢀ1,ꢀseeꢀESIꢀforꢀcompleteꢀsynthesisꢀ
4
7,48
newꢀ applicationsꢀ inꢀ supramolecularꢀ chemistry.
ꢀ Theꢀ procedureꢀ andꢀ characterization).ꢀ Theꢀ ligandꢀ 3ꢀ uponꢀ
fluorinatedꢀ analoguesꢀ ofꢀ hydrocarbonꢀ compoundsꢀ possessꢀ recrystallizationꢀ fromꢀ chloroformꢀ formedꢀ singleꢀ crystalsꢀ
exceptionalꢀ propertiesꢀ suchꢀ asꢀ stericꢀ bulk,ꢀ stiffꢀ andꢀ stableꢀ suitableꢀforꢀX-rayꢀdiffractionꢀanalysis.ꢀAꢀsimilarꢀprocedureꢀwasꢀ
nature,ꢀ simultaneousꢀ hydro-ꢀ andꢀ lipophobicity,ꢀ slowerꢀ followedꢀ forꢀ theꢀ synthesisꢀ ofꢀ theꢀ hydrocarbonꢀ analogueꢀ 3H
aggregationꢀbehaviourꢀandꢀlowerꢀcriticalꢀgelation/aggregationꢀ (seeꢀ ESI).ꢀ However,ꢀ andꢀ notꢀ surprisingly,ꢀ effortsꢀ toꢀ obtainꢀ
concentration.ꢀ Theseꢀ featuresꢀ ofꢀ fluorinatedꢀ counterpartsꢀ singleꢀcrystalsꢀremainedꢀunsuccessful.ꢀInꢀaddition,ꢀligandꢀ ꢀwasꢀ
offerꢀ aꢀ uniqueꢀ opportunityꢀ toꢀ designꢀ materialsꢀ withꢀ preparedꢀ (Fig.ꢀ 1ꢀ andꢀ ESI),ꢀ whichꢀ includesꢀ aꢀ partiallyꢀ
ꢀ
4
4
9
unprecedentedꢀproperties. ꢀInꢀpolymerꢀscience,ꢀpolyethyleneꢀ perfluorinatedꢀ chainꢀ withꢀ anꢀ ethyleneꢀ moietyꢀ betweenꢀ theꢀ
glycolꢀderivativesꢀꢀwithꢀterminalꢀfluoroalkylꢀgroupsꢀhaveꢀshownꢀ carbonylꢀ andꢀ perfluoroꢀ groups.ꢀ Whenꢀ aꢀ knownꢀ amountꢀ ofꢀ
toꢀ exhibitꢀ peculiarꢀ rheologicalꢀ propertiesꢀ asꢀ “associativeꢀ ligandꢀ3ꢀwasꢀdissolvedꢀinꢀdimethylꢀsulfoxideꢀ(DMSO)ꢀbyꢀgentleꢀ
5
0
thickeners”. ꢀSimilarly,ꢀpolyacrylamideꢀwithꢀaꢀminuteꢀamountꢀ heating,ꢀ additionꢀ ofꢀ aꢀ knownꢀ volumeꢀ ofꢀ waterꢀ reachingꢀ
ofꢀ fluorocarbonꢀ groupsꢀ haveꢀ shownꢀ toꢀ associateꢀ muchꢀ DMSO:waterꢀratioꢀofꢀ5:1ꢀ(v/v),ꢀresultedꢀinꢀaꢀviscousꢀprecipitate.ꢀ
5
1
strongerꢀ comparedꢀ toꢀ simpleꢀ hydrocarbonꢀ derivatives. ꢀ Inꢀ However,ꢀ theꢀ viscousꢀ materialꢀ didꢀ notꢀ surviveꢀ duringꢀ theꢀ
999ꢀ Hamiltonꢀ etꢀ al.ꢀ showedꢀ theꢀ gelationꢀ ofꢀ partiallyꢀ gelationꢀtestꢀ(testꢀtubeꢀinversion).ꢀInterestingly,ꢀadditionꢀofꢀ0.5ꢀ
1
5
2
fluorinatedꢀ ureaꢀ derivativesꢀ inꢀ supercriticalꢀ carbonꢀ dioxide. ꢀ molarꢀequivalentꢀofꢀaqueousꢀmetalꢀsaltꢀ(CoCl
2
,ꢀNiCl
ꢀ inꢀ DMSOꢀ resultedꢀ inꢀ immediateꢀ colourꢀ
peptides, bileꢀ acids, ꢀ bis-urea, N-alkylamides, ꢀ geminiꢀ changeꢀfollowedꢀbyꢀprecipitation.ꢀTheꢀcomplexesꢀuponꢀheatingꢀ
2 2
ꢀorꢀFeCl )ꢀ
3
7
Supramolecularꢀ gelsꢀ derivedꢀ fromꢀ fluorinatedꢀ gallicꢀ acid, ꢀ intoꢀ aꢀ solutionꢀ ofꢀ
3
4
0ꢀ
41
42ꢀ
53
5
4
55
phenoxyꢀ units ꢀ andꢀ biphenyl ꢀ haveꢀ beenꢀ reportedꢀ inꢀ theꢀ ledꢀtoꢀaꢀclearꢀsolutionꢀandꢀuponꢀcoolingꢀtoꢀroomꢀtemperatureꢀ
literature.ꢀThisꢀworkꢀshowsꢀhowꢀaꢀsimpleꢀperfluoroalkylamideꢀ stableꢀcolouredꢀgelsꢀwereꢀobtainedꢀ(Fig.ꢀ1,ꢀseeꢀESIꢀforꢀdetails)ꢀ
ofꢀ 4-aminophenyl-2,2´,6,2´-terpyridineꢀ canꢀ actꢀ asꢀ aꢀ showingꢀresistanceꢀtoꢀflowꢀuponꢀtestꢀtubeꢀinversion.ꢀTheꢀgelsꢀ
metallosupramolecularꢀgelator.ꢀTheꢀmetal-ligandꢀcoordinationꢀ underwentꢀ repeatedꢀ sol-gelꢀ transitionꢀ uponꢀ heating-coolingꢀ
ꢀ
Mꢀ=ꢀFe(II),ꢀNi(II) andꢀCo(II)]ꢀcoordinationꢀcomplexꢀ cycles.ꢀ Theꢀ ESI-TOFꢀ massꢀ spectrometryꢀ onꢀ positiveꢀ modeꢀ
leadsꢀtoꢀML
2
ꢀ
[
2
andꢀfluorine-fluorineꢀinteractionsꢀbetweenꢀtheꢀsidechainꢀdriveꢀ revealedꢀ theꢀ formationꢀ ofꢀ ML ꢀ typeꢀ complexesꢀ (seeꢀ ESI),ꢀ
anꢀ extendedꢀ lateralꢀ assembly,ꢀ furnishingꢀ highlyꢀ entangledꢀ supportedꢀ byꢀ NMRꢀ spectroscopyꢀ studies,ꢀ whichꢀ suggestꢀ theꢀ
fibrillarꢀ networks.ꢀ Theꢀ gelationꢀ isꢀ anionꢀ selectiveꢀ andꢀ theꢀ presenceꢀ ofꢀ aꢀ singleꢀ product.ꢀ Inꢀ theꢀ controlꢀ experimentsꢀ
mechanicalꢀandꢀthermalꢀpropertiesꢀcanꢀbeꢀtunedꢀbyꢀchangingꢀ analogousꢀmetalꢀcomplexesꢀcontainingꢀligandꢀ 3Hꢀwereꢀfoundꢀ
theꢀ metalꢀ cation.ꢀ Further,ꢀ theꢀ rheologicalꢀ stepꢀ strainꢀ notꢀtoꢀbeꢀgelators,ꢀtherebyꢀhighlightingꢀtheꢀimportanceꢀofꢀtheꢀ
5
6ꢀ
experimentsꢀshowꢀthatꢀtheꢀgelsꢀundergoꢀaꢀrapidꢀself-healing
recoveringꢀtheꢀgelꢀstrengthꢀafterꢀreleaseꢀofꢀtheꢀstepꢀstrain.ꢀ
perfluoroalkylꢀ unit.ꢀ Theꢀ comparisonꢀ ofꢀ powderꢀ X-rayꢀ
diffractionꢀ (PXRD)ꢀ patternsꢀ ofꢀ 3Hꢀ withꢀ theꢀ simulatedꢀ PXRDꢀ
ꢀ
Resultsꢀandꢀdiscussionsꢀ
patternsꢀusingꢀsingleꢀcrystalꢀX-rayꢀdataꢀofꢀ3ꢀ(Fig.ꢀS9)ꢀrevealedꢀaꢀ
clearꢀdifferenceꢀinꢀtheꢀpackingꢀofꢀtheꢀtwoꢀligands.ꢀ
ꢀ
SynthesisꢀandꢀGelationꢀstudiesꢀ
2
Fig.ꢀ1ꢀSyntheticꢀschemeꢀofꢀligandꢀ3ꢀandꢀitsꢀcomplexationꢀwithꢀM(II)Cl ꢀ(Mꢀ=ꢀNi,ꢀFe,ꢀCo).ꢀPhotographsꢀofꢀ3-Mꢀgels.ꢀChemicalꢀstructureꢀofꢀligandsꢀ3Hꢀandꢀ4.
2
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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Ple aDs ea ꢀl dt oo nꢀ n To rt aꢀ and sj ua sc tt ꢀimo na sr ginsꢀ
JournalꢀNameꢀ
ꢀARTICLEꢀ
Similarly,ꢀwithꢀtheꢀpartiallyꢀfluorinatedꢀsideꢀchainꢀinꢀ4ꢀnoꢀgelationꢀ
wasꢀ observedꢀ byꢀ ligandꢀ itselfꢀ orꢀ uponꢀ complexationꢀ withꢀ FeCl .ꢀ
Interestingly,ꢀligandꢀ4ꢀleadsꢀtoꢀweakꢀgelsꢀuponꢀcomplexationꢀwithꢀ
.5ꢀ eqꢀ ofꢀ CoCl ꢀ (4-Co)ꢀ orꢀ NiCl ꢀ (4-Ni).ꢀ Theꢀ metallogelsꢀ 4-Mꢀ [Mꢀ =ꢀ
View Article Online
DOI: 10.1039/C7DT00983F
2
0
2
2
Co(II)ꢀ orꢀ Ni(II)]ꢀ areꢀ muchꢀ lessꢀ stableꢀ thanꢀ theirꢀ 3-Mꢀ analogues.ꢀ
Indeed,ꢀ4-Coꢀprecipitatesꢀoutꢀafterꢀ6ꢀhoursꢀandꢀ4-Niꢀcrystallizesꢀoutꢀ
afterꢀ 36ꢀ hoursWeꢀ wereꢀ pleasedꢀ toꢀ observeꢀ thatꢀ 4-Niꢀ gelꢀ evolvedꢀ
2 2
intoꢀgoodꢀqualityꢀsingleꢀcrystalsꢀofꢀ[Ni4 ]Cl .ꢀSuchꢀanꢀintriguingꢀgelꢀ
toꢀcrystalꢀtransitionꢀphenomenonꢀhasꢀbeenꢀpreviouslyꢀreportedꢀandꢀ
providesꢀ anꢀ excellentꢀ opportunityꢀ toꢀ investigateꢀ theꢀ potentialꢀ
58
supramolecularꢀ interactionsꢀ thatꢀ causeꢀ theꢀ gelation. ꢀ Carefulꢀ
examinationꢀ ofꢀ theꢀ crystalꢀ supportsꢀ ourꢀ hypothesisꢀ onꢀ
supramolecularꢀpolymerisationꢀthroughꢀF···Fꢀinteractionsꢀduringꢀtheꢀ
gelationꢀandꢀwillꢀbeꢀdiscussedꢀinꢀdetailꢀlater.ꢀFurthermore,ꢀinꢀorderꢀ
toꢀ promoteꢀ polymerizationꢀ andꢀ increaseꢀ theꢀ strengthꢀ ofꢀ theꢀ
supramolecularꢀ structureꢀ byꢀ theꢀ potentialꢀ formationꢀ ofꢀ hydrogenꢀ
bonds,ꢀtheꢀperfluorinatedꢀchainꢀwasꢀattachedꢀviaꢀamideꢀbondsꢀtoꢀ
theꢀphenylterpyridineꢀcore.ꢀTheꢀanionꢀseemsꢀtoꢀplayꢀalsoꢀaꢀcrucialꢀ
roleꢀasꢀonlyꢀchlorideꢀanionsꢀinduceꢀtheꢀgelation,ꢀwhereasꢀtheꢀuseꢀofꢀ
otherꢀ counterꢀ anionsꢀ suchꢀ asꢀ bromide,ꢀ tetrafluoroborate,ꢀ
perchlorate,ꢀtriflateꢀorꢀsulphateꢀdidꢀnotꢀleadꢀtoꢀtheꢀgelꢀformation.ꢀ
Moreꢀ importantly,ꢀ furtherꢀ additionꢀ ofꢀ chlorideꢀ ionsꢀ toꢀ theꢀ non-
gellingꢀ complexesꢀ turnedꢀ onꢀ theꢀ gelation.ꢀ Thisꢀ directlyꢀ providesꢀ
-
evidenceꢀthatꢀtheꢀgelationꢀisꢀCl ꢀspecific.ꢀTheꢀchlorideꢀsaltsꢀofꢀFe(II),ꢀ
Co(II)ꢀ andꢀ Ni(II)ꢀ resultedꢀ inꢀ instantaneousꢀ gelationꢀ atꢀ 2.0ꢀ w/v%ꢀ
ꢀ
(
massꢀofꢀgelatorꢀbyꢀvolumeꢀofꢀsolvent)ꢀandꢀwithꢀaꢀminimumꢀgelationꢀ Fig.ꢀ2ꢀ(A)ꢀCrystalꢀstructureꢀofꢀligandꢀ3ꢀwithꢀthermalꢀdisplacementꢀparametersꢀatꢀ50%ꢀ
probabilityꢀlevel.ꢀ(B)ꢀCrystalꢀpackingꢀofꢀligandꢀ3.ꢀTheꢀlatticeꢀisꢀconstructedꢀfromꢀF···Fꢀ
concentrationꢀ(MGC)ꢀofꢀ<ꢀ1.0ꢀ%.ꢀTheꢀgelꢀmeltingꢀtemperatureꢀ(Tgel)ꢀ
andꢀ thermalꢀ stabilityꢀ measuredꢀ usingꢀ invertedꢀ testꢀ tubeꢀ methodꢀ
showedꢀaꢀlinearꢀincreaseꢀinꢀtheꢀTgelꢀwithꢀincreasingꢀconcentration.ꢀ
However,ꢀforꢀaꢀgivenꢀconcentrationꢀtheꢀgelꢀmeltingꢀtrendꢀfollowedꢀ
theꢀorderꢀFe>Ni>Coꢀ(seeꢀTableꢀ1ꢀandꢀESI).ꢀTheꢀTgelꢀwereꢀsharpꢀforꢀ3-
Feꢀandꢀ3-Coꢀbutꢀ3-Niꢀshowedꢀaꢀbroadꢀrangeꢀofꢀmeltingꢀtemperatureꢀ
interactionsꢀ betweenꢀ theꢀ perfluorinatedꢀ chainsꢀ andꢀ areꢀ reinforcedꢀ byꢀ theꢀ N-H···O=Cꢀ
hydrogenꢀ bondsꢀ betweenꢀ adjacentꢀ moleculesꢀ ofꢀ 3.ꢀ (C)ꢀ Crystalꢀ structureꢀ ofꢀ [Ni4 ]Cl
stabilizedꢀbyꢀN-H···Cl,ꢀπ···πꢀandꢀC-H···πꢀinteractions.ꢀ(D)ꢀCloserꢀviewꢀofꢀ[Ni4 ]Cl2ꢀaroundꢀ
terpyridineꢀcoreꢀtoꢀshowꢀπ···πꢀandꢀC-H···πꢀinteractions.ꢀ(E)ꢀCrystalꢀpackingꢀofꢀcomplexꢀ
Ni4 ]Cl2ꢀviewedꢀalongꢀtheꢀa-axisꢀhighlightingꢀtheꢀF···FꢀandꢀC-F···πꢀinteractions.ꢀꢀ
2
2
ꢀ
2
[
2
(
seeꢀTableꢀS1ꢀandꢀFig.ꢀS11).ꢀꢀ
solid-stateꢀF···Fꢀinteractionꢀactsꢀasꢀoneꢀofꢀtheꢀkeyꢀinteractionsꢀ
inꢀtheꢀformationꢀofꢀtheꢀsupramolecularꢀstructures.ꢀTheꢀpackingꢀ
Tableꢀ1:ꢀGelationꢀresponseꢀofꢀligandsꢀ3ꢀandꢀ3Hꢀtowardsꢀdifferentꢀmetalꢀsaltsꢀatꢀ2ꢀ%ꢀ
aꢀ
DMSOꢀ:ꢀwaterꢀ(5:1ꢀv/v).ꢀGꢀ=ꢀgel,ꢀSꢀ=ꢀsolution.ꢀ Tgelꢀofꢀ2ꢀ%ꢀgels.ꢀ
ofꢀ
3
ꢀ andꢀ itsꢀ solvatesꢀ manifestsꢀ similarꢀ F···Fꢀ interactionsꢀ toꢀ
]Cl ꢀcrystalꢀ(Fig.ꢀ2BꢀandꢀE).ꢀAdditionally,ꢀ
thoseꢀshownꢀbyꢀ[Ni
4
2
2
MetalꢀSaltꢀ
FeCl
CoCl
Ligandꢀ
3
ꢀ
Ligandꢀ3Hꢀ
o
G(70 C) ꢀ
a
theꢀanionꢀselectivityꢀgelationꢀisꢀhighlyꢀsupportedꢀbyꢀtheꢀcriticalꢀ
roleꢀ thatꢀ chlorideꢀ anionsꢀ playꢀ furnishingꢀ theꢀ hydrogenꢀ bondꢀ
2
ꢀ
Sꢀ
Sꢀ
Sꢀ
Sꢀ
Sꢀ
Sꢀ
Sꢀ
Sꢀ
o
G(47 C) ꢀ
a
2
ꢀ
o
G(60 C) ꢀ
a
networkꢀasꢀshownꢀinꢀFig.ꢀ2Eꢀforꢀ[Ni 2
4 ]Cl2.ꢀ
NiCl
2
ꢀ
FeBr
2
ꢀ
Sꢀ
Sꢀ
Sꢀ
Sꢀ
Sꢀ
Morphologyꢀofꢀtheꢀgelsꢀ
4 2
Fe(ClO ) ꢀ
Fe(BF
4 2
) ꢀ
FeSO
4
ꢀ
2
Fe(OTf) ꢀ
ꢀ
SingleꢀcrystalꢀX-rayꢀdiffractionꢀstudyꢀ
SingleꢀcrystalsꢀofꢀgoodꢀqualityꢀforꢀX-rayꢀdiffractionꢀstudiesꢀwereꢀ
obtainedꢀ eitherꢀ inꢀ itsꢀ pureꢀ formꢀ orꢀ asꢀ solvatesꢀ forꢀ ligandꢀ 3ꢀ
uponꢀ slowꢀ evaporationꢀ ofꢀ chloroformꢀ (
tetrahydrofuranꢀ (3·THF)ꢀ andꢀ moistꢀ methanolꢀ (3·CH
solutions.ꢀSystematicꢀanalysisꢀofꢀtheꢀX-rayꢀstructuresꢀ(seeꢀFig.ꢀ
AꢀandꢀBꢀandꢀFigs.ꢀS12-S14)ꢀrevealedꢀaꢀslightlyꢀtwisted,ꢀnon-
linearꢀnatureꢀforꢀtheꢀligandꢀ ꢀandꢀitsꢀabilityꢀtoꢀformꢀhydrogenꢀ
3
ꢀ andꢀ 3·CHCl
3
),ꢀ
3
OH·H
2
O)ꢀ
2
3
bondsꢀ throughꢀ theꢀ amideꢀ group.ꢀ Moreꢀ importantly,ꢀ theꢀ
molecularꢀ packingꢀ alsoꢀ showedꢀ theꢀ extendedꢀ tailꢀ toꢀ tailꢀ
ꢀ
Fig.ꢀ3ꢀScanningꢀelectronꢀmicrographsꢀofꢀdryꢀprecipitateꢀforꢀligandꢀ3ꢀ(A)ꢀandꢀxerogelsꢀꢀꢀꢀꢀꢀ
-Feꢀ(B);ꢀ3-Coꢀ(C)ꢀandꢀ3-Niꢀ(D)ꢀobtainedꢀfromꢀ2ꢀ%ꢀDMSO/H Oꢀsamples.ꢀꢀ
interactionsꢀ ofꢀ theꢀ perfluoroalkylꢀ chainsꢀ inꢀ additionꢀ toꢀ
stackingꢀbetweenꢀtheꢀaromaticꢀmoieties.ꢀTherefore,ꢀinꢀtheꢀꢀ
p-pꢀ
3
2
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ3ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ple aDs ea ꢀl dt oo nꢀ n To rt aꢀ and sj ua sc tt ꢀimo na sr ginsꢀ
Page 4 of 9
ARTICLEꢀ
JournalꢀNameꢀ
View Article Online
DOI: 10.1039/C7DT00983F
ꢀ
Fig.ꢀ4ꢀTransmissionꢀelectronꢀmicrographsꢀofꢀdryꢀprecipitateꢀforꢀ3ꢀ(A&B)ꢀandꢀxerogelsꢀforꢀ
-Feꢀ(C&D);ꢀ3-Coꢀ(E&F)ꢀandꢀ3-Niꢀ(G&H)ꢀobtainedꢀfromꢀ2ꢀ%ꢀDMSO/H Oꢀsamples.ꢀ
3
2
Theꢀ electronꢀ microscopyꢀ ofꢀ dryꢀ precipitatesꢀ ofꢀ ligandꢀ 3ꢀ ꢀ andꢀ
ꢀ
xerogelsꢀ forꢀ metallogelsꢀ 3-Mꢀ [Mꢀ =ꢀ Fe(II),ꢀ Ni(II)ꢀ orꢀ Co(II)]ꢀ areꢀ
1
Fig.ꢀ 5ꢀ Variableꢀ temperatureꢀ NMRꢀ spectroscopyꢀ experiments.ꢀ (A)ꢀ Partialꢀ VTꢀ Hꢀ NMRꢀ
shownꢀinꢀFig.ꢀ3ꢀandꢀ4.ꢀTheꢀscanningꢀelectronꢀmicroscopyꢀ(SEM)ꢀ
2
spectraꢀofꢀ2ꢀ%ꢀDMSO-d6ꢀ-ꢀD Oꢀgelꢀofꢀ3-Fe.ꢀ(B)ꢀPlotꢀshowingꢀchangeꢀinꢀtheꢀchemicalꢀshiftꢀ
1
9
imagesꢀ showedꢀ thatꢀ ligandꢀ 3ꢀ formsꢀ microcrystallineꢀ sheetsꢀ valuesꢀ ofꢀ amideꢀ protonꢀ signalꢀ asꢀ aꢀ functionꢀ ofꢀ temperature.ꢀ (C)ꢀ VTꢀ Fꢀ NMRꢀ ofꢀ 2ꢀ %ꢀ
6 2
DMSO-d ꢀ+ꢀD Oꢀgelꢀofꢀ3-Fe.ꢀ(D)ꢀChangeꢀinꢀtheꢀchemicalꢀshiftꢀvalueꢀofꢀfluorineꢀsignalsꢀasꢀ
severalꢀ micrometersꢀ longꢀ andꢀ 1-2ꢀ µmꢀ wideꢀ (Fig.ꢀ 3A).ꢀ Theꢀ
absenceꢀ ofꢀ interconnectedꢀ networksꢀ isꢀ inꢀ goodꢀ agreementꢀ
aꢀfunctionꢀofꢀtemperature.ꢀ
withꢀtheꢀnon-gellingꢀnatureꢀofꢀ3.ꢀTheꢀSEMꢀmicrographsꢀofꢀgelsꢀ
broadenꢀ (Seeꢀ Fig.ꢀ S17-S20).ꢀ Thisꢀ behaviourꢀ suggestsꢀ aꢀ
thermallyꢀinducedꢀsupramolecularꢀrearrangementꢀofꢀtheꢀmetalꢀ
complexes.ꢀTheseꢀresultsꢀstronglyꢀsupportꢀtheꢀhypothesisꢀofꢀaꢀ
phaseꢀ transitionꢀ observedꢀ inꢀ temperatureꢀ sweepꢀ rheologicalꢀ
derivedꢀ fromꢀ metalꢀ complexesꢀ showedꢀ highlyꢀ entangledꢀ
fibrillarꢀnetworks.ꢀTheꢀdiameterꢀofꢀtheꢀfibersꢀrangeꢀfromꢀ50ꢀtoꢀ
2
00ꢀnmꢀwithꢀindefiniteꢀlength,ꢀoneꢀofꢀtheꢀfeaturesꢀofꢀgelsꢀfromꢀ
1
lowꢀ molecularꢀ weightꢀ gelators.ꢀ Theꢀ transmissionꢀ electronꢀ
measurementsꢀ (seeꢀ nextꢀ section).ꢀ Theꢀ VTꢀ Hꢀ NMRꢀ ofꢀ theꢀ gelꢀ
showedꢀanꢀupfieldꢀshiftꢀ( Ddꢀ=ꢀ0.45ꢀppm)ꢀforꢀamideꢀprotonꢀ(-
microscopyꢀ(TEM)ꢀanalysisꢀofꢀligandꢀ3ꢀshowedꢀtheꢀpresenceꢀofꢀ
microcrystallineꢀstrandsꢀ(Fig.ꢀ4A).ꢀTheꢀxerogelsꢀobtainedꢀfromꢀ NH)ꢀsignalꢀfromꢀ11.79ꢀppmꢀatꢀroomꢀtemperatureꢀ(inꢀgelꢀstate)ꢀ
metallogelsꢀshowedꢀhighlyꢀentangledꢀfibrillarꢀnetworkꢀwhereinꢀ toꢀ11.34ꢀppmꢀuponꢀincreasingꢀtemperatureꢀ(inꢀsolutionꢀstate)ꢀ
theꢀnatureꢀandꢀsizeꢀofꢀtheꢀfibersꢀdependꢀonꢀtheꢀmetalꢀionꢀusedꢀ (Fig.ꢀ5).ꢀItꢀcanꢀbeꢀconcludedꢀthatꢀhydrogenꢀbondingꢀisꢀoneꢀofꢀ
5
6ꢀ
inꢀ theꢀ studyꢀ (Fig.ꢀ 4B-D).ꢀTheꢀfiberꢀdiameterꢀvariedꢀ fromꢀ 100- theꢀ drivingꢀ forcesꢀ involvedꢀ inꢀ self-assembly. Further,ꢀ theꢀ
1
25ꢀnmꢀforꢀ3-Fe,ꢀ80-100ꢀnmꢀforꢀ3-Coꢀandꢀtoꢀ50-100ꢀnmꢀforꢀ3- Fourierꢀ transformꢀ infraredꢀ (FT-IR)ꢀ spectroscopyꢀ studiesꢀ
supportꢀthisꢀobservation.ꢀTheꢀFT-IRꢀspectrumꢀofꢀtheꢀbulkꢀsolidꢀ
ꢀ wasꢀ comparedꢀ toꢀ theꢀ xerogelꢀ ofꢀ aggregatesꢀ ofꢀ ꢀ andꢀ
metallogelsꢀ3-Mꢀ(Mꢀ=ꢀFe,ꢀCo,ꢀNi).ꢀTheꢀspectrumꢀofꢀbulkꢀsolidꢀ
Ni.ꢀꢀ
3
3
ꢀ
3
ꢀ
Variableꢀtemperatureꢀ(VT)ꢀNMRꢀꢀ
-
1ꢀ
showedꢀamideꢀ-NHꢀstretchingꢀatꢀ3323ꢀcm whichꢀshiftsꢀtoꢀ3245ꢀ
-1
5
9
60
Solution, ꢀ andꢀ solidꢀ state, ꢀ NMRꢀ spectroscopyꢀ experimentsꢀ cm ꢀ forꢀ theꢀ xerogels,ꢀ clearlyꢀ indicatingꢀ theꢀ presenceꢀ ofꢀ
haveꢀ beenꢀ extensivelyꢀ usedꢀ toꢀ studyꢀ interactions,ꢀ structuralꢀ hydrogenꢀbondꢀthroughꢀtheꢀamideꢀmoietiesꢀ(SeeꢀFig.ꢀS26).ꢀInꢀ
1
9
changesꢀ andꢀ dynamicsꢀ ofꢀ gelation.ꢀ However,ꢀ NMRꢀ orderꢀ toꢀ investigateꢀ theꢀ roleꢀ ofꢀ fluorineꢀ aꢀ VTꢀ Fꢀ NMRꢀ
1
9
spectroscopicꢀcharacterizationꢀofꢀcertainꢀmetalꢀcomplexesꢀisꢀaꢀ experimentꢀ wasꢀ performed.ꢀ Theꢀ Fꢀ signalsꢀ underwentꢀ aꢀ
challengingꢀ taskꢀ dueꢀ toꢀ theꢀ paramagneticꢀ natureꢀ ofꢀ theseꢀ progressiveꢀbroadeningꢀandꢀdownfieldꢀshiftꢀuponꢀtemperatureꢀ
species.ꢀTherefore,ꢀoutꢀofꢀtheꢀthreeꢀmetalꢀcomplexes,ꢀtheꢀ3-Feꢀ increaseꢀ (Fig.ꢀ 5C).ꢀ Evenꢀ though,ꢀ theꢀ changeꢀ inꢀ theꢀ chemicalꢀ
gelꢀ wasꢀ selectedꢀ forꢀ NMRꢀ studiesꢀ dueꢀ toꢀ theꢀ diamagneticꢀ shiftꢀ valueꢀ isꢀ onlyꢀ 0.2ꢀ ppm,ꢀ itꢀ isꢀ significantꢀ consideringꢀ theꢀ
4
0,61
characterꢀofꢀtheꢀFe(II)-terpyridineꢀlowꢀspinꢀcomplexes.ꢀInꢀmoreꢀ strengthꢀ ofꢀ theꢀ F···Fꢀ interaction.
detail,ꢀ2.0ꢀ%ꢀDMSO-d -D
Oꢀgelꢀofꢀ3-Feꢀwasꢀanalysedꢀbyꢀvariableꢀ employedꢀ toꢀ investigateꢀ theꢀ influenceꢀ ofꢀ gelationꢀ onꢀ theꢀ C-Fꢀ
temperatureꢀ(VT)ꢀ HꢀNMRꢀinꢀaꢀtemperatureꢀintervalꢀfromꢀ30ꢀtoꢀ stretchingꢀfrequency,ꢀwhichꢀisꢀusuallyꢀfoundꢀinꢀtheꢀrangeꢀ1000-
ꢀ Further,ꢀ FT-IRꢀ wasꢀ
6
2
1
o
o
-1
9
0 Cꢀwithꢀ5 Cꢀincrements.ꢀTheꢀbroadꢀsignalsꢀinꢀtheꢀgelꢀstateꢀatꢀ 1400ꢀ cm .ꢀ Theꢀ C-Fꢀ stretchingꢀ frequencyꢀ forꢀ bulkꢀ solidꢀ 3ꢀ
roomꢀ temperatureꢀ turnedꢀ sharperꢀ untilꢀ theꢀ temperatureꢀ exhibitedꢀtwoꢀnarrowꢀpeaksꢀatꢀ1200ꢀandꢀ1144ꢀcm .ꢀHowever,ꢀ
reachedꢀ 50 C.ꢀ Surprisingly,ꢀ atꢀ 55 Cꢀ theꢀ signalsꢀ turnedꢀ broadꢀ forꢀtheꢀcaseꢀofꢀtheꢀmetallogelsꢀ3-Mꢀ(Mꢀ=ꢀFe,ꢀCo,ꢀNi),ꢀtheꢀformerꢀ
again,ꢀ however,ꢀ furtherꢀ increaseꢀ inꢀ temperatureꢀ aboveꢀ 55 Cꢀ signalꢀledꢀtoꢀaꢀbroadꢀbandꢀpeakingꢀatꢀ1198ꢀcm ꢀmeanwhileꢀtheꢀ
ledꢀtoꢀsharpꢀpeaks.ꢀAꢀmoreꢀaccurateꢀstudyꢀwasꢀperformedꢀbyꢀ latterꢀresolvedꢀintoꢀtwoꢀpartiallyꢀmergedꢀsignalsꢀatꢀ 1146ꢀandꢀ
heatingꢀtheꢀgelꢀsampleꢀfromꢀ40ꢀtoꢀ70 Cꢀwithꢀ2 Cꢀincrements.ꢀItꢀ 1130ꢀcm (SeeꢀFig.ꢀS27).ꢀTheseꢀresultsꢀcertainlyꢀindicateꢀthatꢀ
wasꢀ foundꢀ thatꢀ theꢀ transitionꢀ appearedꢀ atꢀ 58 C.ꢀ ꢀ Further,ꢀ aꢀ theꢀfluorineꢀatomsꢀplayꢀanꢀessentialꢀroleꢀonꢀtheꢀpolymerizationꢀ
controlledꢀ coolingꢀ rampꢀ (sol-gel)ꢀ wasꢀ performedꢀ fromꢀ 85ꢀ toꢀ process, ꢀ inꢀ excellentꢀ agreementꢀ withꢀ theꢀ conclusionsꢀ
0 C.ꢀꢀUponꢀcoolingꢀtheꢀsignalsꢀbecameꢀbroaderꢀuntilꢀ55 Cꢀandꢀ obtainedꢀbyꢀVTꢀ FꢀNMR.ꢀThisꢀstronglyꢀsuggestsꢀtheꢀexistenceꢀ
-1
o
o
o
-1
o
o
-1ꢀ
o
4
0
o
o
19
3
belowꢀ55 Cꢀtheyꢀturnedꢀsharperꢀandꢀonceꢀagainꢀcontinuedꢀtoꢀꢀ
o
ofꢀrobustꢀF···Fꢀinteractionsꢀinꢀtheꢀgelꢀstate.ꢀ
4
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
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Ple aDs ea ꢀl dt oo nꢀ n To rt aꢀ and sj ua sc tt ꢀimo na sr ginsꢀ
JournalꢀNameꢀ
ꢀARTICLEꢀ
certainꢀtemperatureꢀcanꢀbeꢀfittedꢀtoꢀvan’tꢀHoffꢀeVqiewuaAtrtiioclenOꢀ(nEliqne.ꢀ
DOI: 10.1039/C7DT00983F
1
ꢀ
).ꢀ
ꢀ
ꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢁꢂ(ꢃꢄꢁ) = (−∆ꢅdissꢀ/ꢆꢇeqꢀ) + (∆ꢃdissꢀ/ꢆ) ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ(1)ꢀ
whereꢀ∆Hdissꢀandꢀ∆Sdissꢀareꢀenthalpyꢀandꢀentropyꢀofꢀdissolution,ꢀ
respectively.ꢀ Theꢀ Teqꢀ isꢀ theꢀ equilibriumꢀ temperatureꢀ andꢀ Rꢀ isꢀ
theꢀgasꢀconstant.ꢀTheꢀgelationꢀprocessꢀ(whichꢀisꢀtheꢀoppositeꢀ
ꢀ
Fig.ꢀ 6ꢀ Determinationꢀ ofꢀ thermodynamicꢀ parameters.ꢀ (A)ꢀ Concentrationꢀ ofꢀ liquid-likeꢀ ofꢀtheꢀdissolutionꢀprocess)ꢀisꢀenthalpicallyꢀfavourableꢀ(ΔHdissꢀ=ꢀꢀ
-
1
phaseꢀfreeꢀgelatorꢀasꢀaꢀfunctionꢀofꢀtemperatureꢀdeterminedꢀusingꢀfluorobenzeneꢀasꢀanꢀ
externalꢀstandardꢀinꢀ2ꢀ%ꢀDMSO-d ꢀ+ꢀD Oꢀgelꢀofꢀ3-Fe.ꢀ(B)ꢀVantꢀHoff´sꢀtreatmentꢀofꢀVTꢀ
3
1(1)ꢀ kJꢀ mol )ꢀ andꢀ entropicallyꢀ disfavourableꢀ (ΔSdiss=ꢀ 58(4)ꢀ Jꢀ
-1ꢀ -1
mol K )ꢀ asꢀ expectedꢀ forꢀ anꢀ assemblyꢀ ofꢀ orderedꢀ fibersꢀ
6
2
NMRꢀdata,ꢀln(solubility)ꢀagainstꢀinverseꢀofꢀtemperature.ꢀ
5
throughꢀ hydrogenꢀ bondingꢀ andꢀ F···Fꢀ interactions. ꢀ Theꢀ valueꢀ
5
-
1
Aꢀ carefullyꢀ designedꢀ NMRꢀ spectroscopyꢀ experimentꢀ canꢀ
ꢀ
ofꢀtheꢀfreeꢀenergyꢀisꢀΔGdissꢀ=ꢀ13(2)ꢀkJꢀmol . Moreover,ꢀaꢀparallelꢀ
provide,ꢀ notꢀ onlyꢀ theꢀ gelꢀ meltingꢀ temperatureꢀ andꢀ structuralꢀ van’tꢀHoffꢀstudyꢀwasꢀperformedꢀbyꢀmonitoringꢀsignalꢀintensityꢀ
1
9
informationꢀaboutꢀsupramolecularꢀinteractionsꢀresponsibleꢀofꢀ ofꢀtheꢀgelatorꢀusingꢀVTꢀ FꢀNMR.ꢀTheꢀthermodynamicalꢀvaluesꢀ
1
9
gelation,ꢀ butꢀ alsoꢀ theꢀ concentrationꢀ ofꢀ theꢀ aggregatedꢀ andꢀ obtainedꢀ byꢀ applyingꢀ van’tꢀ Hoffꢀ treatmentꢀ toꢀ VTꢀ Fꢀ NMRꢀ
-
1
-1ꢀ -1
non-aggregatedꢀ components,ꢀ enthalpy,ꢀ entropyꢀ andꢀ freeꢀ (ΔHdissꢀ=ꢀ29(1)ꢀkJꢀmol ,ꢀΔS =ꢀ51(4)ꢀJꢀmol K ꢀandꢀΔGdissꢀ=ꢀ13(2)ꢀ
dissꢀ
-
1
energyꢀ ofꢀ gelation.ꢀ Itꢀ hasꢀ beenꢀ arguedꢀ thatꢀ theꢀ NMRꢀ kJꢀmol )ꢀareꢀinꢀaꢀgoodꢀagreementꢀwithꢀtheꢀvaluesꢀobtainedꢀbyꢀ
1
VTꢀ HꢀNMRꢀ(SeeꢀESI).ꢀToꢀtheꢀbestꢀofꢀourꢀknowledge,ꢀthisꢀisꢀtheꢀ
resonancesꢀobservedꢀinꢀaꢀgel-phaseꢀatꢀroomꢀtemperatureꢀareꢀ
largelyꢀ resultingꢀ fromꢀ theꢀ freeꢀ moleculesꢀ (mobile,ꢀ non-
aggregatedꢀ components),ꢀ whereasꢀ theꢀ aggregatedꢀ
firstꢀexampleꢀwhereꢀthermodynamicꢀparametersꢀofꢀtheꢀsol-gelꢀ
ꢀ
19
transitionꢀareꢀobtainedꢀthroughꢀVTꢀ FꢀNMRꢀspectroscopy.ꢀ
5
9,62
componentsꢀareꢀNMRꢀsilent.
ꢀExperimentalꢀquantificationꢀisꢀ
ꢀ
Rheologicalꢀpropertiesꢀꢀ
oftenꢀachievedꢀusingꢀaꢀstandardꢀandꢀmonitoringꢀtheꢀintensityꢀ
ofꢀ theꢀ observedꢀ gelatorꢀ signal.ꢀ Inꢀ ourꢀ experimentꢀ
fluorobenzeneꢀ wasꢀ usedꢀ asꢀ externalꢀ standardꢀ inꢀ orderꢀ toꢀ Inꢀ orderꢀ toꢀ understandꢀ theꢀ mechanicalꢀ propertiesꢀ andꢀ
quantifyꢀ theꢀ ratioꢀ betweenꢀ aggregatedꢀ andꢀ non-aggregatedꢀ responseꢀtoꢀmechanicalꢀstimuliꢀrheologicalꢀmeasurementsꢀforꢀ
fractionꢀinꢀtheꢀ3-Feꢀgelꢀuponꢀincreasingꢀtheꢀtemperature.ꢀTheꢀ aggregatesꢀofꢀ3ꢀandꢀgelsꢀ3-Fe,ꢀ3-Coꢀandꢀ3-Niꢀwereꢀcarriedꢀoutꢀ
o
o
experimentsꢀ wereꢀ performedꢀ fromꢀ 20ꢀ toꢀ 100 Cꢀ withꢀ 5 Cꢀ (Fig.ꢀ 7).ꢀ First,ꢀ theꢀ sol-gelꢀ transitionꢀ wasꢀ investigatedꢀ byꢀ usingꢀ
increment.ꢀWhenꢀtheꢀconcentrationꢀofꢀtheꢀfreeꢀmoleculesꢀ(inꢀ oscillatoryꢀtimeꢀsweepꢀexperimentꢀwithꢀ2ꢀ%ꢀgelsꢀfromꢀ20ꢀminꢀ
mM)ꢀ wasꢀ plottedꢀ againstꢀ theꢀ temperatureꢀ aꢀ steadyꢀ increaseꢀ toꢀ 2ꢀ h.ꢀ Theꢀ timeꢀ sweepꢀ experimentsꢀ wereꢀ performedꢀ withinꢀ
o
o
untilꢀ 60 Cꢀ wasꢀ observedꢀ (Fig.ꢀ 6A).ꢀ Aboveꢀ 60 Cꢀ theꢀ theꢀ viscoelasticꢀ regimeꢀ (10ꢀ %ꢀ strain)ꢀ withꢀ 6.2ꢀ rad/sꢀ underꢀ
concentrationꢀ remainedꢀ constantꢀ indicatingꢀ thatꢀ aꢀ gel-solꢀ controlledꢀ temperatureꢀ (Fig.ꢀ 7A).ꢀ Thisꢀ experimentꢀ allowsꢀ theꢀ
o
transitionꢀ occursꢀ atꢀ 60 Cꢀ andꢀ allꢀ theꢀ componentsꢀ areꢀ gelationꢀkineticsꢀasꢀthereꢀwillꢀbeꢀaꢀrapidꢀchangeꢀinꢀtheꢀstorageꢀ
disassembled.ꢀThisꢀtemperatureꢀisꢀslightlyꢀlowerꢀthanꢀtheꢀTgelꢀꢀ
(G’)ꢀandꢀlossꢀmodulusꢀ(G’’)ꢀuponꢀgelꢀformation.ꢀOnꢀtheꢀotherꢀ
3-Feꢀ=ꢀ69 C)ꢀobtainedꢀbyꢀplacingꢀaꢀsealedꢀgelꢀsampleꢀ hand,ꢀitꢀalsoꢀprovidesꢀinformationꢀrelatedꢀtoꢀtheꢀtimeꢀrequiredꢀ
upside-downꢀ inꢀ aꢀ thermallyꢀ controlledꢀ oilꢀ bath,ꢀ increasingꢀ toꢀformꢀaꢀstableꢀgel.ꢀTheꢀelasticꢀmodulusꢀG´ꢀforꢀfreeꢀligandꢀ
ꢀ
o
valueꢀ(Tgel
ꢀ
3
ꢀ
temperatureꢀ andꢀ assigningꢀ theꢀ Tgelꢀ asꢀ theꢀ temperatureꢀ atꢀ wasꢀfoundꢀtoꢀbeꢀ0.2ꢀkPaꢀwhichꢀisꢀanꢀorderꢀofꢀmagnitudeꢀlowerꢀ
whichꢀtheꢀgelꢀstartsꢀtoꢀflow.ꢀInꢀsuchꢀexperiments,ꢀdoneꢀinꢀanꢀoilꢀ thanꢀ thatꢀ ofꢀ theꢀ metallogels.ꢀ Amongꢀ metallogelsꢀ theꢀ gelꢀ
bath,ꢀ theꢀ oilꢀ temperatureꢀ mightꢀ slightlyꢀ differꢀ fromꢀ theꢀ formationꢀ followsꢀ theꢀ orderꢀ Fe>Co~Niꢀ withꢀ elasticꢀ moduliꢀ 3-
temperatureꢀofꢀtheꢀgelꢀinsideꢀtheꢀtestꢀtube.ꢀAdditionally,ꢀtheꢀ Ni(1.6ꢀ kPa)>3-Co(1.4ꢀ kPa)>3-Feꢀ (0.7ꢀ kPa)ꢀ (Fig.ꢀ 7A).ꢀ Theꢀ
conditionsꢀ inꢀ whichꢀ theꢀ gelꢀ undergoesꢀ transformationꢀ intoꢀ aꢀ frequencyꢀ sweepꢀ experimentsꢀ showedꢀ thatꢀ G´ꢀ ofꢀ theꢀ gelsꢀ isꢀ
solutionꢀ areꢀ different,ꢀ thereforeꢀ enablingꢀ smallꢀ deviationꢀ higherꢀthanꢀG´´,ꢀconfirmingꢀthatꢀtheꢀmaterialsꢀunderꢀstudyꢀareꢀ
withinꢀtheꢀTgelꢀmeasurementsꢀthroughꢀdifferentꢀmethods.ꢀWithꢀ viscoelasticꢀsolidsꢀ(Fig.ꢀ7B).ꢀTheꢀgel-solꢀtransitionꢀwasꢀfollowedꢀ
increasingꢀ temperatureꢀ theꢀ gelꢀ fibersꢀ disassembleꢀ dueꢀ toꢀ usingꢀ temperatureꢀ sweepꢀ rheologicalꢀ experimentꢀ (Fig.ꢀ 7C).ꢀ
thermalꢀ motionꢀ formingꢀ non-aggregatedꢀ materialꢀ andꢀ Temperatureꢀrampsꢀfromꢀ20ꢀtoꢀ90ꢀ°Cꢀwereꢀperformedꢀwithꢀaꢀ5ꢀ
thereforeꢀ sharperꢀ peaks.ꢀ Theꢀ processꢀ ofꢀ disassemblyꢀ canꢀ beꢀ °C/minꢀheatingꢀrate.ꢀUnlikeꢀmanyꢀsupramolecularꢀgels,ꢀwhichꢀ
consideredꢀ asꢀ aꢀ solubilizationꢀ process;ꢀ therefore,ꢀ theꢀ van´tꢀ showꢀ rapidꢀ changesꢀ inꢀ theirꢀ elasticꢀ moduliꢀ uponꢀ gel-solꢀ
HoffꢀtreatmentꢀofꢀtheꢀVTꢀNMRꢀdataꢀcanꢀbeꢀappliedꢀ(SeeꢀFig.ꢀ6Bꢀ transition,ꢀtheꢀgelsꢀhereꢀshowedꢀsomeꢀuniqueꢀproperties:ꢀtheyꢀ
1
7,63
andꢀ ESI).
solubleꢀ ifꢀ theyꢀ areꢀ observableꢀ byꢀ NMRꢀ andꢀ formꢀ insolubleꢀ moduliꢀofꢀgelsꢀdecreasedꢀrapidlyꢀbyꢀtwoꢀordersꢀofꢀmagnitudeꢀ
ꢀ Theꢀ gelatorꢀ moleculesꢀ areꢀ consideredꢀ toꢀ beꢀ manifestedꢀ two-stepꢀ meltingꢀ behaviour,ꢀ whereꢀ theꢀ elasticꢀ
o
o
o
aggregatesꢀ ifꢀ theyꢀ areꢀ NMRꢀ silent.ꢀ Theꢀ dataꢀ suitableꢀ forꢀ theꢀ atꢀ aroundꢀ 45 C,ꢀ 35 Cꢀ andꢀ 55 Cꢀ forꢀ 3-Fe,ꢀ 3-Coꢀ andꢀ 3-Niꢀ
van’tꢀHoffꢀtreatmentꢀcomeꢀfromꢀtheꢀmeasurementsꢀmadeꢀwellꢀ respectivelyꢀ(Fig.ꢀ7C).ꢀFurtherꢀheatingꢀresultedꢀinꢀplateausꢀforꢀ5ꢀ
o
belowꢀ Tgelꢀ andꢀ aboveꢀ MGCꢀ inꢀ orderꢀ toꢀ avoidꢀ initialꢀ stepsꢀ ofꢀ -ꢀ 10 Cꢀ beforeꢀ completeꢀ melting.ꢀ Thisꢀ canꢀ beꢀ ascribedꢀ toꢀ theꢀ
gelation.ꢀ ΔHdissꢀ andꢀ ΔSdissꢀ areꢀ assumedꢀ toꢀ beꢀ temperatureꢀ structuralꢀ re-organizationꢀ ofꢀ theꢀ gelꢀ networkꢀ andꢀ theꢀ roleꢀ ofꢀ
independent.ꢀ Forꢀ anꢀ idealꢀ solution,ꢀ theꢀ solubilityꢀ (sol)ꢀ atꢀ aꢀ severalꢀweakꢀinteractionsꢀresponsibleꢀofꢀgelationꢀasꢀshownꢀbyꢀ
theꢀVTꢀNMRꢀstudies.ꢀTheꢀinitialꢀresponseꢀcanꢀbeꢀattributedꢀtoꢀꢀ
Thisꢀjournalꢀisꢀ©ꢀTheꢀRoyalꢀSocietyꢀofꢀChemistryꢀ20xxꢀ
J.ꢀName.,ꢀ2013,ꢀ00,ꢀ1-3ꢀ|ꢀ5ꢀ
Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Ple aDs ea ꢀl dt oo nꢀ n To rt aꢀ and sj ua sc tt ꢀimo na sr ginsꢀ
Page 6 of 9
ARTICLEꢀ
JournalꢀNameꢀ
1
9
Fꢀ VTꢀ NMRꢀ resonancesꢀ revealꢀ thatꢀ gelationꢀ isꢀVeienwtAhrtaicllpeiOcnallinlyeꢀ
DOI: 10.1039/C7DT00983F
favourableꢀ andꢀ entropicallyꢀ disfavourable.ꢀ Theꢀ excellentꢀ
1
19
agreementꢀ betweenꢀ theꢀ resultsꢀ obtainedꢀ byꢀ Hꢀ andꢀ Fꢀ VTꢀ
NMRꢀdemonstrateꢀtheꢀversatilityꢀofꢀdifferentꢀspinꢀactiveꢀnucleiꢀ
inꢀ determiningꢀ thermodynamicꢀ parametersꢀ andꢀ couldꢀ beꢀ
furtherꢀ employedꢀ inꢀ supramolecularꢀ gelsꢀ lackingꢀ hydrogenꢀ
atoms.ꢀ Metallogelsꢀ undergoꢀ step-wiseꢀ meltingꢀ behaviourꢀ asꢀ
1
suggestedꢀ byꢀ Hꢀ NMRꢀ andꢀ supportedꢀ byꢀ rheologicalꢀ
measurements.ꢀ Moreꢀ interestingly,ꢀ metallogelsꢀ exhibitꢀ self-
healingꢀ propertiesꢀ underꢀ step-strainꢀ rheologicalꢀ experiment.ꢀ
Repeatedꢀcyclesꢀofꢀhigh-lowꢀstrainꢀwereꢀappliedꢀtoꢀmetallogels.ꢀ
AꢀdecreaseꢀofꢀthreeꢀordersꢀofꢀmagnitudeꢀonꢀtheꢀvaluesꢀofꢀG’ꢀ
turnsꢀ intoꢀ aꢀ fastꢀ strengthꢀ recoveryꢀ (self-healing)ꢀ uponꢀ
removingꢀtheꢀstrain.ꢀOurꢀresultsꢀsuggestꢀthatꢀincorporationꢀofꢀ
fluorineꢀatomsꢀinduceꢀmetallogelationꢀwithꢀnovelꢀthermalꢀandꢀ
mechanicalꢀproperties.ꢀ
ꢀ
Fig.ꢀ7ꢀRheologicalꢀpropertiesꢀofꢀ2ꢀ%ꢀDMSO/H
2
Oꢀgelsꢀderivedꢀfromꢀgelators.ꢀ(A)ꢀTimeꢀ
sweepꢀ experiments.ꢀ (B)ꢀ Frequencyꢀ sweep.ꢀ (C)ꢀ Temperatureꢀ sweepꢀ experiments.ꢀ (D)ꢀ
Stepꢀstrainꢀexperimentsꢀdemonstratingꢀfastꢀself-healing.ꢀ
Acknowledgementsꢀ
theꢀ weakeningꢀ ofꢀ theꢀ F···Fꢀ interactions,ꢀ followedꢀ byꢀ aꢀ
disruptionꢀ ofꢀ theꢀ H-bondingꢀ network.ꢀ Thenꢀ theꢀ step-strainꢀ
experimentꢀwasꢀperformedꢀinꢀorderꢀtoꢀinvestigateꢀtheꢀgel-solꢀ
transitionꢀ andꢀ self-healingꢀ understoodꢀ asꢀ theꢀ gelꢀ strengthꢀ
recovery,ꢀunderꢀseveralꢀcycles.ꢀForꢀtheꢀstepꢀstrainꢀexperimentsꢀ
controlledꢀ strainsꢀ ofꢀ 0.1ꢀ %ꢀ andꢀ 150ꢀ %ꢀ wereꢀ cycledꢀ forꢀ 60ꢀ s,ꢀ
respectively.ꢀ Theꢀ gelsꢀ showedꢀ rapidꢀ responseꢀ toꢀ increasedꢀ
strainꢀbyꢀturningꢀintoꢀviscoelasticꢀliquidsꢀindicatedꢀbyꢀtheꢀrapidꢀ
decreaseꢀinꢀG´ꢀbyꢀthreeꢀordersꢀofꢀmagnitudeꢀandꢀwellꢀbelowꢀ
thatꢀ ofꢀ G´´ꢀ (Fig.ꢀ 7D).ꢀ Theꢀ applicationꢀ ofꢀ increasedꢀ strainꢀ alsoꢀ
appearsꢀ toꢀ breakꢀ theꢀ structureꢀ furtherꢀ duringꢀ theꢀ 60ꢀ sꢀ
experimentꢀ asꢀ shownꢀ byꢀ graduallyꢀ decreasingꢀ elasticꢀ moduliꢀ
values.ꢀUponꢀswitchingꢀtoꢀlowerꢀstrainꢀtheꢀgelsꢀrecoverꢀmostꢀofꢀ
theirꢀ originalꢀ mechanicalꢀ strengthꢀ almostꢀ instantlyꢀ i.e.ꢀ rapidꢀ
self-healing.ꢀ Additionally,ꢀ theꢀ processꢀ canꢀ beꢀ repeatedꢀ asꢀ
shownꢀ inꢀ Figureꢀ 7D.ꢀ However,ꢀ slightlyꢀ lowerꢀ elasticꢀ moduliꢀ
afterꢀ firstꢀ high-lowꢀ strainꢀ cycleꢀ andꢀ gradualꢀ build-upꢀ isꢀ
observed,ꢀ thereforeꢀ indicatingꢀ thatꢀ theꢀ structureꢀ build-upꢀ toꢀ
equilibriumꢀstateꢀwouldꢀrequireꢀlongerꢀperiodsꢀofꢀ“rest”ꢀ(lowꢀ
strain).ꢀꢀ
Theꢀ Academyꢀ ofꢀ Finlandꢀ (KRꢀ grantꢀ no’s.ꢀ 263256,ꢀ 265328ꢀ andꢀ
2
92746),ꢀ Centreꢀ ofꢀ Excellenceꢀ inꢀ Molecularꢀ Engineeringꢀ ofꢀ
Biosyntheticꢀ Hybridꢀ Materialsꢀ (HYBER,ꢀ 2014-2019),ꢀ ERCꢀ
Advancedꢀ Grantꢀ MIMEFUN,ꢀ AXAꢀ fundsꢀ andꢀ theꢀ Universityꢀ ofꢀ
Jyväskyläꢀ areꢀ kindlyꢀ acknowledgedꢀ forꢀ theꢀ financialꢀ support.ꢀ
Thisꢀ workꢀ madeꢀ useꢀ ofꢀ theꢀ Aaltoꢀ Universityꢀ Nanomicroscopyꢀ
Centerꢀ(Aalto-NMC)ꢀfacilities.ꢀꢀ
ꢀ
Notesꢀandꢀreferencesꢀ
1
2
3
4
5
6
7
8
9
1
1
1
S.ꢀ J.ꢀ Dalgarno,ꢀ N.ꢀ P.ꢀ Powerꢀ andꢀ J.ꢀ L.ꢀ Atwood,ꢀ Coord.ꢀ Chem.ꢀ
Rev.,ꢀ2008,ꢀ252,ꢀ825-841.ꢀ
B.ꢀ H.ꢀ Northrop,ꢀ Y.-R.ꢀ Zheng,ꢀ K.-W.ꢀ Chiꢀ andꢀ P.ꢀ J.ꢀ Stang,ꢀ Acc.ꢀ
Chem.ꢀRes.,ꢀ2009,ꢀ42,ꢀ1554-1563.ꢀ
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T.ꢀR.ꢀCook,ꢀY.ꢀR.ꢀZhengꢀandꢀP.ꢀJ.ꢀStang,ꢀChem.ꢀRev.,ꢀ2013,ꢀ113,ꢀ
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7
J.ꢀ Zhangꢀ andꢀ C.-Y.ꢀ Su,ꢀ Coord.ꢀ Chem.ꢀ Rev.,ꢀ 2013,ꢀ 257,ꢀ 1373-
1408.ꢀ
P.ꢀ Mal,ꢀ B.ꢀ Breiner,ꢀ K.ꢀ Rissanenꢀ andꢀ J.ꢀ R.ꢀ Nitschke,ꢀ Science,ꢀ
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009,ꢀ324,ꢀ1697-1699.ꢀ
K.ꢀ Suzuki,ꢀ M.ꢀ Tominaga,ꢀ M.ꢀ Kawanoꢀ andꢀ M.ꢀ Fujita,ꢀ Chem.ꢀ
Commun.,ꢀ2009,ꢀ1638-1640.ꢀ
M.ꢀ Fujita,ꢀ J.ꢀ Yazakiꢀ andꢀ K.ꢀ Ogura,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.,ꢀ 1990,ꢀ
Conclusionsꢀ
Inꢀconclusion,ꢀweꢀhaveꢀpresentedꢀaꢀsimpleꢀterpyridineꢀligandꢀ
decoratedꢀ withꢀ aꢀ perfluoroalkylꢀ chainꢀ thatꢀ leadsꢀ toꢀ
metallosupramolecularꢀgelsꢀinꢀaqueousꢀdimethylꢀsulfoxide.ꢀOurꢀ
workꢀdemonstratesꢀtheꢀimportanceꢀofꢀnotꢀonlyꢀtheꢀfluorineꢀ-ꢀ
fluorineꢀ interactionsꢀ butꢀ alsoꢀ theꢀ hydrogenꢀ bondingꢀ andꢀ theꢀ
counterꢀ anion.ꢀ Onlyꢀ chlorideꢀ inducesꢀ theꢀ gelation,ꢀ thereforeꢀ
beingꢀ anionꢀ specificꢀ withꢀ potentialꢀ useꢀ inꢀ molecularꢀ
recognition.ꢀFurther,ꢀweꢀshowedꢀthatꢀmorphological,ꢀthermalꢀ
andꢀmechanicalꢀpropertiesꢀdependꢀonꢀtheꢀnatureꢀofꢀtheꢀmetalꢀ
1
12,ꢀ5645-5647ꢀ.ꢀ
M.ꢀFujita,ꢀY.ꢀJ.ꢀKwon,ꢀS.ꢀWashizuꢀandꢀK.ꢀOgura,ꢀJ.ꢀAm.ꢀChem.ꢀ
Soc.,ꢀ1994,ꢀ116,ꢀ1151-1152.ꢀ
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EddaoudiꢀandꢀJ.ꢀKim,ꢀNature,ꢀ2003,ꢀ423,ꢀ705-714.ꢀ
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8
55-859.ꢀ
ion.ꢀ Indeed,ꢀ SEMꢀ andꢀ TEMꢀ imagesꢀ showꢀ clearꢀ differencesꢀ onꢀ 13 D.ꢀFujita,ꢀK.ꢀSuzuki,ꢀS.ꢀSato,ꢀM.ꢀYagi-Utsumi,ꢀY.ꢀYamaguchi,ꢀN.ꢀ
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theꢀ sizeꢀ andꢀ morphologyꢀ ofꢀ theꢀ gelꢀ fibers.ꢀ Additionally,ꢀ 3-Fe
ꢀ
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3-Niꢀ >ꢀ 3-Coꢀ >ꢀ 3-Fe.ꢀ Thermodynamicꢀ parametersꢀ ofꢀ
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Pleaseꢀdoꢀnotꢀadjustꢀmarginsꢀ

Dalton Transactions
Page 8 of 9
View Article Online
DOI: 10.1039/C7DT00983F
Metal complexes from a perfluoroalkylamide terpyridine self-assemble into anion
selective gels, which manifest self-healing and thermal rearrangement in aqueous-
dimethyl sulfoxide.

Page 9 of 9
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT00983F
TOC figure