简介:SpectroscopicmethodsareusedtoinvestigatecoordinationstructureofN-picolylpolyurethanetransitionmetalcomplexes(PUPYM,M=Co^2+andNi^2+).Geometricalarrangementofligandsinfirst-shellcoordinationsphereofmetalionsispostulatedtobetetrahedralCoL2Cl2andoctahedralNiL2-Cl2Z2.whereListhepicolylgroupandZisahydrate.FromextendedX-rayabsorptionfinestructure(EXAFS)analysis,bondlengthsformetal-chlorineandmetal-ligandofPUPYMaresimilartothoseofsmallmolecularweighttransitionmetalcomplexes.Atwo-phasemodelofPUPYMwhichbestdescribestheexperimentaldataofDMTAandSAXS.isproposed.Onemicrophaseistheharddomainofselfsegregatedhaedsegmentsbroughtaboutbymetal-ligandinteraction.andtheotherphaseisthematrixofsoftsegments.Transitionmetalion-ligandmoietiesandtheirinteractionsdominatethemacroscopicthermalbehaviorofPUPYM.Theligandfieldstabilizationenergydifference(ΔLFSE)betweenmteald-electronsincomplexeswithtwopicolylligandsinthecoordinationsphereofmetalionsandcomplexesmaintainingonepicolylligandascoordinationpendentgroupiscalculatedonthebasisofobservedcoordinationstructure,anditrepresentstheenergysuppliedtosplitcoordinationcross-links.ΔLFSEofpolyurethanenickel(II)complexislargerthanthatofthecobalt(II)complex,Sincethemobilityofhardsegmentsisininverseproportiontothestrengthofcoordinationcross-links.ahigherα-transitiontemperatureofPUPYNi^2+withrespecttoPUPYCo^2+isfoundasexpected.