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Incorporating MM Quadruple Bonds Into Conjugated Organic Oligomers: Syntheses and Optoelectronic Properties
Author(s) -
Chisholm Malcolm H.
Publication year - 2012
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201100656
Subject(s) - chemistry , electron paramagnetic resonance , conjugated system , metal , carboxylate , infrared spectroscopy , photochemistry , valence (chemistry) , polymer chemistry , polymer , metal ions in aqueous solution , spectroscopy , crystallography , stereochemistry , organic chemistry , nuclear magnetic resonance , physics , quantum mechanics
Metal–metal (MM) quadruply bonded units supported by four carboxylate ligands MM(O 2 CR) 4 , where MM = Mo 2 , MoW, or W 2 react with dicarboxylic acids or monocarboxylic acids to generate compounds of the form [(RCO 2 ) 3 MM] 2 (O 2 C–X–CO 2 ) (I), and trans ‐MM(O 2 CR) 2 (O 2 C–X) 2 (II), where X is a π‐conjugated group, under appropriate conditions. (I) and (II) provide model compounds for extended‐chain polymers/oligomers of formula [(RCO 2 ) 2 MM(O 2 C–X–CO 2 )] (III). Oxidation of (I) and reduction of (II) lead to mixed valence (MV) metal‐ and organic‐centered ions, respectively, which have been characterized by electron paramagnetic resonance and UV–Vis–near infrared spectroscopy. Photochemical excitation of compounds (I) and (II) leads to metal–ligand charge transfer states. Time‐resolved infrared spectroscopy has been employed to determine the charge distribution and dynamics in the S 1 and T 1 states.