TY - JOUR
T1 - Optical and thermal charge-transfer processes occurring in a series of three-centered, cyanide-bridged intervalent charge-transfer complexes
AU - Pfennig, Brian W.
AU - Bocarsly, Andrew Bruce
PY - 1992/1/1
Y1 - 1992/1/1
N2 - The mixed-valent compound {Pt(NH3)4}2{(NC)5Fe-CN-Pt(NH 3)4-NC-Fe(CN)5} was used as the starting point for the synthesis and characterization of two series of trinuclear "M-Pt-M" compounds. The first group of complexes have the general formula Na2{L(NC)4Fe-CN-Pt(NH3) 4-NC-Fe(CN)4L} (where the sixth coordination site on the terminal iron units has been varied using six different substituted pyridine or pyrazine ligands, L), and the secondary group of compounds have the general formula {Pt(NH3)4}2{(NC)5M-CN-Pt(NH 3)4-NC-M(CN)5} (where M = Fe, Ru, and Os). All of the compounds yielded an absorption spectrum containing an intervalent charge-transfer (IT) band in the visible. Both series of complexes were modeled using Marcus-Hush theory to estimate the reorganization energies for the optical electron-transfer processes, electron-transfer rate constants, thermal-activation barriers, and the degrees of delocalization of these species. In addition, the kinetics of formation, photochemical decomposition, and a novel solvent-gated charge-transfer process are discussed.
AB - The mixed-valent compound {Pt(NH3)4}2{(NC)5Fe-CN-Pt(NH 3)4-NC-Fe(CN)5} was used as the starting point for the synthesis and characterization of two series of trinuclear "M-Pt-M" compounds. The first group of complexes have the general formula Na2{L(NC)4Fe-CN-Pt(NH3) 4-NC-Fe(CN)4L} (where the sixth coordination site on the terminal iron units has been varied using six different substituted pyridine or pyrazine ligands, L), and the secondary group of compounds have the general formula {Pt(NH3)4}2{(NC)5M-CN-Pt(NH 3)4-NC-M(CN)5} (where M = Fe, Ru, and Os). All of the compounds yielded an absorption spectrum containing an intervalent charge-transfer (IT) band in the visible. Both series of complexes were modeled using Marcus-Hush theory to estimate the reorganization energies for the optical electron-transfer processes, electron-transfer rate constants, thermal-activation barriers, and the degrees of delocalization of these species. In addition, the kinetics of formation, photochemical decomposition, and a novel solvent-gated charge-transfer process are discussed.
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U2 - 10.1021/j100180a044
DO - 10.1021/j100180a044
M3 - Article
AN - SCOPUS:0000237321
SN - 0022-3654
VL - 96
SP - 226
EP - 233
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 1
ER -