含吡啶、咪唑组装单元的合成及其自组织结构的研究

20005252000612Synthesisandself-assemblystructuresofassemblyunitcomprisingpyridineorimidazolself-assemblyassemblyunitnetwork65NNNHNHH2CCOCOH2C(4)(dmppa)NHCONHCONN(2)(dppa)NHOOH(1)(dppy)OOONHNHNHNNNCCC(3)(tppa)-Cu2+Co2+Ni2+Mn2+Ag+Au2+dppydppy2Cu2py2dppy4Cu4dppatppa1dppy2Cu2py2dppy2Cu2py2Cu2+,Cu2+OCu2-O2ÅÅÅdppy4Cu4dppy4Cu4Cu2+NNHNNHCOCO(9)(dqpa)(TPH)CHCHCH222NNNNNN(7)(5)(tmppa)OOONHNHNHCCCNNN2CH2CH2CHNNNNCHCH22(6)(bix)NNNNCH2£¨£©4(8)(dib)Cu2+Cu2+Cu2+OCu4-O6ÅÅÅ3.dppadppaN-HNÅÅÅ4.tppaN-HN10ÅÅÅÅSynthesisandself-assemblystructursofassemblyunitcomprisingpyridineorimidazolAbstractBidentateorpolydentateligandswhichcontainpyridineorimidazolareofconsiderablecurrentinterestasefficientcoordinationdonorsets.Ligandscontainingtwoormorecoordinationatomcancombinetransition-metalandbuildblocksbyweakintermolecularforcessuchashydrogenbonding-stacking.Inthiscontext,usingthedonorsetssuchaspyridineandimidazol,consideringvariousweakinteractions(hydrogenbonding-stackingvanderwaalsionicandchargetransferinteractionsandmetalcomplexation)wedesignandsynthesisninebidentateorpolydentateligands.NNNHNHH2CCOCOH2C(4)(dmppa)NHCONHCONN(2)(dppa)NHOOH(1)(dppy)OOONHNHNHNNNCCC(3)(tppa)Usingtheseligandswestudytheself-assemblyreactions(ligands-transitionmetal(Cu2+Co2+Ni2+Mn2+Ag+Au2+)ligands-organicmolecularligands-ligands).WhenliganddppyreactswithCu2+underdifferentenvironments,weachievedtwodifferentcomplexesdppy2Cu2py2anddppy4Cu4.Undervapordiffusion,wegotsinglecrystals.Wealsogetsinglecrystalsofdppaandtppabyvolatilizingsolvent.1.Structureofdppy2Cu2py2dppy2Cu2py2istwo-nuclearcomplex.Thecoordinationnumberofcopperisfive.Inthecentrosymmetriccomplexoneligandisassociatedwitheachcopperandthephenolatesarebridging,givingaCu2-O2core;theremainingonecoordinationsitesareoccupiedbypyridine.Thereisnot-stackingeffectinthissinglecrystal.Itsparametersofunitcellarefollowing.MonodinicCrystalSystem,SpacegroupP2(1)/nR=0.0392UnitCelldimensionsa=13.3302Åb=9.36129Åc=14.676211ÅNNHNNHCOCO(9)(dqpa)(TPH)CHCHCH222NNNNNN(7)(5)(tmppa)OOONHNHNHCCCNNN2CH2CH2CHNNNNCHCH22(6)(bix)NNNNCH2£¨£©4(8)(dib)=90=100.949=902.Structureofdppy4Cu4dppy4Cu4isfour-nuclearcomplex.Therearetwokindsofcoordinativeformsofcopper.Thecoordinationnumberofcentercopperisfour.Butthatoftheothercopperisfive.Twokindsofcoppersarelinkedthroughathree-bridge-oxygengivingaCu4-O6core.Thereisa-stackingeffectinthissinglecrystalresultinaone-dimensionallinearstructure.Itsparametersofunitcellarefollowing.MonodinicCrystalSystem,SpacegroupP2(1)/nR=0.0735UnitCelldimensionsa=13.3356Åb=14.83513Åc=15.49210Å=90=97.555=903.StructureofdppaTheconformationofthesinglecrystalisanti.Adjacentmoleculararelinkedwithhydrogenbonding(N-HN)Resultinatwo-dimensionalnetwork.Therearerectangulararteriesacrossnetwork.Thereisnot-stackingeffectbetweenthestages.Hydrogenbondingisthemostimportantfactortobuildblock.Itsparametersofunitcellarefollowing.MonodinicCrystalSystem,SpacegroupP2(1)/nR=0.0500UnitCelldimensionsa=5.792012Åb=16.6392Åc=8.302810Å=90=109.68711=904.StructureoftppaAdjacentmoleculararelinkedwithhydrogenbonding(N-HN)Resultinatwo-dimensionalnetwork.Therearehoneycomdarteriesacrossnetwork.Thereisnot-stackingeffectbetweenthestages.Hydrogenbondingisthemostimportantfactortobuildblock.Itsparametersofunitcellarefollowing.MonodinicCrystalSystem,SpacegroupC2/cR=0.1147UnitCelldimensionsa=26.4865Åb=15.3324Åc=15.9934Å=90=126.892=90Synthesisandself-assemblystructuresofassemblyunitcomprisingpyridineorimidazol200051dppy2dppa3tppa4dmppa5tmppa6bix7tph8dib9dqpa678-Cu2+Co2+Ni2+Mn2+Ag+Au2+Adppy2Cu2py2Bdppy4Cu4CdppaDtppaDppyCuCu-Odppy4Cu419dppy2Cu2py218dppy4Cu425dppa34tppa415456596266-[1][2]—--Sd-dM–-WardNO[3—8][9][10][11][12]PP2BedppyBFNO-NONN[13][141516]HL1Ni[14]1HL1Cu[15]2HL1Mn[14]3NNHOHL1NHOHL2NNHOHL3NNNHOOH42HL123Cu[17—20]Cu[2122][23]LiangPingWuCu(ClO4)2.6H2O[23]DuncanMnBF42[24]HoskinsAgNO3[25]O-HO,N-HO,C-HO,N-HN[26]4[27]5:NNNNCH2CH2NNNNCH2£¨£©4NNNNCH2CH2NHCOCONHOHOHNNCOOHCOOH.HOOC45--(1)(dppy)(2)dppa(3)(tppa)(4)(dmppa)5)(tmppa)NHOOHNHCONHCONNOOONHNHNHNNNCCCNNNHNHH2CCOCOH2COOONHNHNHCCCNNN2CH2CH2CH(6)(bix)(7)(8)(dib)(9)(dqpa)-Cu2+,Co2+,Ni2+,Mn2+,Ag+,Au2+1.(dppy)2Cu2(py)2Cu2+dppy(dppy)2Cu2(py)2Cu2+O2.(dppy)4Cu4Cu2+dppyDMF(dppy)4Cu4Cu2+ONNNNCHCH22(TPH)CHCHCH222NNNNNNNNNNCH2£¨£©4NNHNNHCOCO3.dppadppaDMFN-HN4.tppatppaDMFN-HN10Å1.dppy1.11.2THF2-26-Aldrich1.31.3.1N23.8ml40mlTHF1Mg11.3.2330mlTHFN270mlTHF12NH4Cl50mlPH=31.3.3dppyN23.02003KOHCH2Cl2CH2Cl2BrBr+MgTHFBrOCHMgBrOCHNOCHCHONHOOHPy.HCl3333¡æ2525¡æ200¡æNBrOCH3NOCHCHO33MS70evm/e263246235218207192180170NMR80MHZCDCl36.85-7.128HAr7.491H7.582H10.282HNH2dppa2.12.2A.RFluca—A.RFlucaA.R2.32.10.0106mol50mlCHCl320.0213mol-30mlCHCl3-8MS70evm/e318*M+2422251983tppa3.13.2A.RFluca—A.RFlucaA.RClCl+CHClNNNHNH+2HCl3COCONNH22COCO»ØÁ÷»ØÁ÷+CHCl+HCl33NNH2OOOClClClOOONHNHNHNNNCCCCCC33.34-4.70.05mol100ml3.980.015mol50ml4-82.9745.2%MS70evm/e438M+362*3182862424dmppa4.14.2A.RFluca4—A.RFlucaA.R4.34-4.540.042mol40mlCHCl314-4.060.02mol100mlCHCl318NaOHPH5.4378.4%MS70evm/e346M+255239212*NMR80MHZCD32SO4.544HMe7.334HPy8.014HAr8.524HPy9.082HNH5tmppa5.1ClCl+2