What determines the solvatochromism of metal-to-ligand charge transfer transitions? A demonstration involving 17 tungsten carbonyl complexes

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Journal of Organometallic Chemistry, 321 (2): 215--226 (1987)
DOI: 10.1016/0022-328X(87)85041-6


A consistent model which permits rationalization and estn. of the solvatochromic behavior of coordination compds. with metal-to-ligand charge transfer (MLCT) absorption bands is described. The model shows how the changing relationship between metal-ligand bond polarities in the ground and MLCT excited state dets. whether neg., pos., or no solvatochromism results. Data for 17 mononuclear and binuclear tetra- and pentacarbonyltungsten complexes were analyzed in order to illustrate and substantiate the different electronic situations leading to various degrees of solvatochromism. Ligand basicities, calcd. HMO coeffs., ESR coupling consts., and metal fragment oxidn. potentials were used to est. the ability of metal fragments and ligands for charge transfer in the excited state and the resulting solvatochromism of complexes. on SciFinder(R)



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