鋯簇金屬有機(jī)骨架材料的合成總結(jié)

序號配體條件結(jié)構(gòu)來源1N人N <0 0(200mg),H3TATB(60mg)andtrifluoroaceticacidin12mLofDEFwereultrasonicallydissolvedinaPyrexvial.Themixturewasheatedat120°Cinanovenfor12h.Aftercoolingdowntoroomtemperature, white powder crystallineprecipitatewasharvestedbyfiltration?K.PCN-7772Allsamplesweresynthesizedviaarefluxmethod involving the reaction of2-sulfoterephthalicacidwithZrClinwaterunderrelativelyconcentratedconditions.Forthesamplewithnoadditivesduringsynthesis(1),monosodium2-sulfoterephthalicacid(5g,mmol)wasdissolvedinminimalwater,andthe]passedthroughDOWEX50WX8protonexchangeresintoobtain2-sulfoterephthalicacid.Thewaterwasthenremovedbyrotaryevaporation,n(

then40mLoffreshultrapurewaterwasaddedtodissolvethesolid.Separately,ZrClg,mmol)wasdissolvedin15mLofultrapurewater(caution,highlyexothermic),thenthetwosolutionsweremixedtomakeaclear,slightlypinksolutionwithpH<1.Thesolutionwasthenheatedtoreflux,andafter~3minutesawhiteprecipitateformed.Refluxwascontinuedfor16hours,thenthesolutionwascooledandthesolidwasrecoveredbycentrifugation.Thesolidwasthenwashed2xwithultrapurewaterthenrefluxedforanother16hoursinultrapurewatertopurify.Synthesisof14nmUiO-66-N3納米級別(Zr6O4OH4(C8H3O4-N3)62-Azido-1,4-benzenedicarboxylicacid(50mg,mmol)wasdissolvedin1mLofN,NDimethylformamide(DMF).Inaseparatevial,zirconylchlorideoctahydrate(21

'mg,mmol)wasdissolvedin3mLofDMF.Thetwsolutionsweremixedtogetherina10mLscintillationvial,andaceticacid(300M)wasaddedtothereactionmixture.Thesolutionwasheatedat90Cfor18htoyieldUiO-66-N3(Zr6O4OH4(C8H3O4-N3)6.MOFnanoparticleswerepurifiedbycentrifugation(15000rpm,90min)followedbysolventexchange(3xDMFand3xNANOpureH2O)overa48hperiod.MOFnanoparticlesweresuspendedinH2Oforcharacterizationandfunctionalizationwitho?4-DUT-67.ZrCl/HfCl(230mg/320mg,1mmol)wasdissolvedinthemixtureofDMFmL)andNMPmL)b：sonicationfor10min.2,5-Thiophenedicarboxylicacid(Htdc)(110mg,mmol)wasaddedtoresultingsolutionandsonicatedadditional5min.Afterthataceticacid(7mL,*r117mmol)wasaddedtothesolutionandsonicatedfor10min.Theresultingmixturewasdistributedto10Pyrextubes,whichweresubsequentlytemperedat120°Cfor48h.TheresultedpowderwasseparatedbycentrifugationandwashedseveraltimeswithDMFuntilsupernatantsolutionbecamecolorless.Thepowderwasfilteredanddriedunderargonatmosphereforhalfanhour.Yield:224mg%)forDUT-67(Zr)and259mg%)forDUT-67(Hf).ThesinglecrystalsofDUT-67wereobtainedusingthesameprocedure,but10mLofaceticacidinsteadof7mLwereadded.ZrCl/HfCl(230mg/320mg,1mmol)wasdissolvedinDMF(25mL)bysonicationfor10min.Htdc(258mg,mmol)wasaddedtoresultingsolution,andthemixturewassonicatedadditional5min.Afterthataceticacid(11mL,183mmol)wasaddedandthemixturewassonicatedforfurther10min.Thereactionmixturewasdistributedto12Pyrextubes,whichweresubsequentlytemperedat120°Cfor72h.ThewashinganddryingprocedurewasthesameasappliedtoDUT-67.Yield:384mg%)forDUT-67(Zr)and453mg%)forDUT-67(Hf).ThesinglecrystalsofDUT-68(Zr)wereobtainedusingthesamesyntheticprotocol,bututilizinglargeramountofmodulator.Chem.Sci.,2015, 6,3466Chem.Sci.,2015, 6,3466-3470|3467AsolutionofHeddb(65mg,,ZrCl(60mg,,(HOAc)in16mLofN,N-dimethyl-formamide(DMF)wassealedina20mLglassvialandheatedat1201CwashedwithDMFandacetone,andthendriedinair(yield72mg).ZrCl(24mg)wasdissolvedin8mLofN,N-dimethylformamide(DMF)ina25mLpyrexvial,towhichbenzoicacidwasadded.Themixturewasheatedin85°Covenfor1hoursandcooledtotheroomtemperature.Then,HTBPP(20mg)wasaddedtotheabovesolution,whichwas(sonicatedforawhile.Theresultingmixturewasheatedin120°Covenfor96hourstoyieldabout14mgofdarkredcrystals(yield:%basedonHTBPP).ThecrystalsobtainedwerefilteredandwashedwithDMF.Elementalanalysescalcd(%)

forFJI-H6(Afteractivationandabsorbedsmallamountofwater,thecrystalhasaformulof[ZrO(OH)(HTBPP)]?~2OnHO):a&(V分11l-Ofi.oo6薩奪亨■60巧 COaMCQjH村u血由MBPV.MOF,ZrCbi：10ing)商艮BPV(10嶂：iw氾血渤1叫in5ml^fDhlF^]idOO&iiaLofiiLlluDrtiKecic/目叩昭a(bǔ)iiledTlie^elujtiaii腕烏rheiili^xdIdI.OO^CftM'5d盯，Ida^ocdahiulE(1)pale件而尊園id?tieMOFpfodiwt(y^]ii]0mgMP"syttibeshoruiBFV mliu^jiugLh，isi‘v<5臥§).由id1「』頓.削標(biāo)冊翼1址代？1.卜1」?biplbemyl410weftdi&slwdin』5iuLofDMF心D嶺mLofiijfti!Of<w<ik同1中1TbrwIwkqw^kih?nhEEra1Mtfw5Jnys問3flhidawhit-r皿網(wǎng)牛園1網(wǎng)叫]襯將■h&MQFptpAici[yiM1Jcn*，4#“?KMf-1UiO-66agZrOCl2*8H2Owasdissolvedin20mlDMF/mlHAcunder5minsonication.Terephthalicacidg,mmol,eq)wasaddedandthemixturewas

sonicatedfor5minmoreandplacedinto120Cpreheatedovenfor1day.Solutionwasdecanted/centrifuged,precipitatewaswashedDMF4timesandacetone4timesover12hours.Thmaterialwasevacuated12hatRTfollowedby12hat120C(ramp1C/min).UiO-66b?gZrOCl2*8H2Owasdissolvedin32mlDMF/3gbenzoicacidunder5minsonication.Terephthalicacidg,mmol,eq)wasaddedandthemixturewassonicatedfor5minmore,distributedto4vialsandplacedinto120Cpreheatedovenfor1day.Precipitatewasfiltered,washede

DMF4timesandacetone4timesover12hours.Thematerialwasevacuated12hatRTfollowedby12hat120C(ramp1C/min).Yieldoftheactivatedmaterial-g.UiO-66fgZrOCl2*8H2Owasdissolvedin20mlDMF/mlHCOOHunder5minsonication.Terephthalicacidg,mmol,eq)wasaddedandthemixturewassonicatedfor5minmoreandplaced[into120Cpreheatedovenfor1day.Solutioiwasdecanted/centrifuged,precipitatewaswashedDMF4timesandacetone4timesover12hours.Thematerialwasevacuated12hatRTfollowedbyn

12hat120C(ramp1C/min).Yieldoftheactivatedmaterial-g.UiO-66hgZrOCl2*8H2Owasdissolvedin40mlDMF/ml(10eq)HClunder5minsonication.Terephthalicacidg,mmol,1eq)wasaddedandthemixturewassonicatedfor5minmorandplacedinto120Cpreheatedovenfor1day.Precipitatewasfiltered,washedDMF,DMF/NEt3/H2O(20/ml),DMF2timesandacetone4timesover6hours.Thematerialwasevacuated4hat70C@followedwith15hat150C(ramp1C/min).Yieldoftheactivatedmaterial-g.UiO-67ae

gZrOCl2*8H2Owasdissolvedin20mlDMF/mlHAcunder5minsonication.4,4'-biphenyldicarboxylicacidg,mmol,eq)wasaddedandthemixturewassonicatedfor5minmoreandplacedinto120Cpreheatedoveifor1day.Solutionwasdecanted/centrifuged,precipitatewaswashedDMF4timesandacetone4timesover12hours.Thematerialwasevacuated19hatRTfollowedby6hat100C(ramp1C/min).Yieldoftheactivatedmaterial-g.S4:UiO-67bgZrOCl2*8H2Owasdissolvedin32mlDMF/3n

gbenzoicacidunder5minsonication.4,4'-biphenyldicarboxylicacidg,mmol,eq)wasaddedandthemixturewassonicatedfor5minmore,distributedto4vialsandplacedinto120Cpreheatedovenfor1day.Precipitatedwasfiltered,washedDMF4timesandacetone4timesover12hours.Thematerialwasevacuated19hatRTfollowedby6hat100C(ramp1C/min).Yieldoftheactivatedmaterial-g.UiO-67fgZrOCl2*8H2Owasdissolvedin100mlDMF4mlHCOOHunder5minsonication.4,4'-(biphenyldicarboxylicacid(1g)wasaddedandthemixturewassonicatedfor5minmoreand

placedinto120Cpreheatedovenfor1day.Precipitatewasfine-filtered/centrifuged,washedDMF4timesandacetone5timesover4hours.Toremovesolventsfromporesthematerialwasevacuated12hatRTfollowedwith12hat120C(ramp1C/min).Yieldoftheactivatedmaterial-g.UiO-67hgZrOCl2*8H2Owasdissolvedin40mlDMF/ml(10eq)HClunder5minsonication.4,4'-biphenyldicarboxylicacidg,mmol,1eq)wasaddedandthemixturewassonicatedfor5minmoreandplacedinto120Cpreheatedoveifor1day.Precipitatewasfiltered,washedDMF,n

#DMF/NEt3/H2O(20/ml),DMF2timesandacetone4timesover6hours.Thematerialwasevacuated4hat70Cfollowedwith15hat120C(ramp1C/min).Yieldoftheactivatedmaterial-g.UiO-67tgZrOCl2*8H2Owasdissolvedin20mlDMF/mlTFAunder5minsonication.4,4'-biphenyldicarboxylicacidg,mmol,eq)wasaddedandthemixturewassonicatedfor5minmoreandplacedinto120Cpreheatedoveifor1day.Solutionwasdecanted/centrifuged,precipitatewaswashedDMF4timesandacetone4timesover12hours.Thematerialwasevacuatedn

19hatRTfollowedby6hat100C(ramp1C/min).Yieldoftheactivatedmaterial-g.#UiO-68agZrOCl2*8H2Owasdissolvedin10mlDMF/mlHAcunder5minsonication.2',5'-dimethyl-[pterphenyl]-4,4''-dicarboxylicacidg,1eq)wasaddedandthemixturewassonicatedfor5minmoreandplacedinto120Cpreheatedovenfo:1day.Solutionwasdecanted/centrifuged,precipitatewaswashedDMF4timesandacetone4timesover12hours.Thematerialwasevacuated1hatRTfollowedby6hat100C(ramp1C/min).Yieloftheactivatedmaterial-g.r9dUiO-68bgZrOCl2*8H2Owasdissolvedin16mlDMF/g

benzoicacidunder5minsonication.2',5'-}dimethyl-[p-terphenyl]-4,4''-dicarboxylicacidg)wasaddedandthemixturewassonicatedfor5minmore,distributedto2vialsandplacedinto120Cpreheatedovenfor1day.Precipitatewasfiltered,washedDMF4timesandacetone4timesover12hours.Thematerialwasevacuated19hatRTfollowedby6hat100C(ramp1C/min).Yieldoftheactivatedmaterial-g.S5UiO-67Cr53mgofCrCl3*3THFwasdissolvedin8mlDCM

andfiltered.50mgofactivatedUiO-67wasaddedtothesolutionandsoakedovernight.ThesolutionwasdecantedandprecipitatewaswashedwithDCM5itimesduring1d.Thematerialwasevacuated12hatRTfollowedby6hat100C(ramp1C/min).UiO-66Cr40mgofCrC】3*3THFwasdissolvedin6mlDCMandfiltered.64mgofactivatedUiO-66Fwa:addedtothesolutionandsoakedovernight.ThesolutionwasdecantedandprecipitatewaswashedwithDCM5timesduring1d.Thematerialwasevacuated12hatRTfollowedby6hat100C(ramps

1C/min).~MOF-525Zr6(OH)4O4(C48N4O8H26)3Zirconylchlorideoctahydratemg,mmol)wasaddedtoN,N-dimethylformamide(DMF,10mL)andsonicatedforthirtyminutes.Followingsonication,tetrakis(4-carboxyphenyl)porphyrinmg,mmol)wasaddedtothesolution.Aftertenminutesfurthersonication,aceticacidmL)wasaddedtothesolution.Thesolutionwasplacedina20mLscintillationvialandheatedat65°Cforthreedays.ThemicrocrystallinepowderwasfilteredandwashedwithDMF(5X10mL)overathree-hourperiod.TheDMFwasthenreplacedwithacetone(5X30mL)overafivedayperiod.Finally,thevolatileacetonewasremovedbyheatingat120°Cundervacuum(30mTorr)for48hrs.MOF-525-CuZr6(OH)4O4(C48N4O8H24Cu)3W)°MMM

Zirconylchlorideoctahydratemg,mmol)wasaddedtoDMF(10mL)andsonicatedforthirtyminutes.Followingsonication,Cu(II)meso-tetra(4-carboxyphenyl)porphyrinmg,mmol)wasaddedtothesolution.Aftertenminutesfurthersonication,aceticacidmL)wasaddedtothesolution.Thesolutionwasplacedina20mLscintillationvialandheatedat65°Cforthreedays.ThemicrocrystallinepowderwasfilteredandwashedwithDMF(5X10mL)overathree-hourperiod.TheDMFwasthenreplacedwithacetone(5X30mL)overafivedayperiod.Finally,thevolatileacetonewasremovedbyheatingat120°Cundervacuum(30mTorr)for48hrs.S4MOF-535Zr6O4(OH)4(C36O8H20)3Zirconiumtetrachloridemg,mmol)andaceticacid(2mL)wereaddedtoDMF(10mL)andsonicatedforthirtyminutesina20mL

scintillationvial.4,4'-((1E,1'E)-(2,5-bis((4-carboxyphenyl)ethynyl)-1,4-phenylene)bis(ethene-2,1-diyl))dibenzoicacid)(H4-XF,16mg,mmol)addedtothesolutionanddissolvedbysonication.Thereactionwasheatedat60°Cfor4hrs,followedbyheatingat120°Cfortwodays,Thesinglecrystalswerecollectedbyfiltration,andwashedwithDMF(5X10mL.overathree-hourperiod.TheDMFwasthenreplacedwithacetone(5X30mL)overafive-dayperiod.Finally,thevolatileacetonewasremovedbyheatingat100°Cundervacuum(30mTorr)for20hrs.)MOF-545Zr6(H2O)8O8(C48N4O8H26)2Zirconylchlorideoctahydratemg,mmol)wasaddedtoDMF(10mL)andsonicatedforthirtyminutes.Followingsonication,tetrakis(4-carboxyphenyl)porphyrinmg,mmol)wasaddedtothesolution.Aftera

furthertenminutesofsonication,formicacid(7mL)wasaddedtothesolution.Thesolutionwasplacedintwo20mLscintillationvialsandheatedat130°Cforthreedays.ThesinglecrystalswerecollectedbyfiltrationandwashedwithDMF(5X10mL)overathree-hourperiod.TheDMFwasthenreplacedwithacetone(5X30mL)overafive-dayperiod.Finally,thevolatileacetonewasremovedbyheatingat120°Cundervacuum(30mTorr)for48hrs.MOF-545-FeZr6(H2O)8O4(C48N4O8H24FeCl)2Zirconylchlorideoctahydratemg,mmol)wasaddedtoDMF(10mL)andsonicatedforthirtyminutes.Followingsonication,Fe(III)meso-tetra(4-carboxyphenyl)porphyrinchloridemg,mmol)wasaddedtothesolution.Afterafurthertenminutesofsonication,formicacid(5mL)wasaddedtothesolution.Thesolutionwasplacedintw<)

20mLscintillationvialsandheatedat130°Cforthreedays.S5ThesinglecrystalswerecollectedbyfiltrationandwashedwithDMF(5X10