Electronic localization versus delocalization: a dimetal approach

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dc.contributor.advisor Cotton , F . Albert en_US
dc.contributor.committeeMember Fackler , John P . en_US
dc.creator Liu , Chun Yuan en_US
dc.date.accessioned 2006 -08 -16T19 :08 :31Z
dc.date.accessioned 2014 -02 -19T19 :25 :43Z
dc.date.available 2006 -08 -16T19 :08 :31Z
dc.date.available 2014 -02 -19T19 :25 :43Z
dc.date.created 2003 -05 en_US
dc.date.issued 2006 -08 -16T19 :08 :31Z
dc.identifier.uri http : / /hdl .handle .net /1969 .1 /3903
dc.description.abstract A series of dimolybdenum compounds having a Mo2 4+ core coordinated by various ligands , including formamidinate (e .g . DAniF = N , NN -di -p -ansisylformamidinate ) , acetate and /or acetonitrile molecules , have been synthesized as building blocks for the construction of Mo2 -containing supramolecular arrays . Compound Mo2 (DAniF )3 (O2CCH3 ) was specifically designed for the preparation of dimolybdenum pairs , whereas the others meet the needs of Mo2 4+ units for different geometry settings . Compounds described by a general formula [Mo2]L[Mo2] , where [Mo2] = [Mo2 (DAniF )3]+ , have two dimetal units electronically coupled by the central unit L , which consequently engender significant impact on the redox property and electronic structure of the molecule . It is found that in the weakly coupled complex system , [Mo2]M (OCH3 )4[Mo2] (M = Zn and Co ) , the mixed -valence complexes present asymmetric molecular structures with two distinct [Mo2] units corresponding to be a bond order 4 .0 (F2B4*2 ) and 3 .5 (F2B4*1 ) , respectively . EPR and magnetic susceptibility measurements for the doubly oxidized species show that there is no significant antifferromagnetic spin coupling . Electron delocalization occurs in the complex system where a N , N' -dimethyloxamidate binds two [Mo2] units within two fused six -membered rings . In this case , the mixed -valence complex has a symmetric molecular structure , implying that the odd electron is fully delocalized over two [Mo2]units . Strong metal -metal interaction is also evidenced by intervalence charge transfer of the mixed -valence species and the diamanetism of the doubly oxidized complex . Remarkably , two isomers varying in linkage conformation , namely , alpha and beta , have been isolated as diaryloxamidate ligands are used as the linker . Studies on the neutral and the oxidized compounds of the two isomers by employing various techniques consistently show that in the alpha form intramolecular electron transfer is blocked , while in the beta form , the electrons are delocalized over the two [Mo2] units . Thus , the mixed -valence complexes of the two isomers are appropriately described by alpha -[Mo2]0 (oxamidate )[Mo2]1+ and beta - [Mo2]0 .5+ (oxamidate )[Mo2]0 .5+ respectively . en_US
dc.format.extent 1560056 bytes
dc.format.medium electronic en_US
dc.format.mimetype application /pdf
dc.language.iso en _US en_US
dc.publisher Texas A &M University en_US
dc.subject Electron delocalization en_US
dc.title Electronic localization versus delocalization : a dimetal approach en_US
dc.type Book en
dc.type.genre Electronic Dissertation en_US
dc.type.material text en_US
dc.format.digitalOrigin born digital en_US

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Electronic localization versus delocalization: a dimetal approach. Available electronically from http : / /hdl .handle .net /1969 .1 /3903 .

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