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Title: Luminescence and intramolecular energy-transfer processes in isomeric cyano-bridged Rhenium(I)-Rhenium(I) and Rhenium(I)-Ruthenium(II)-Rhenium(I) polypyridyl complexes

Abstract

Mixed-metal and homometal cyano-bridged polypyridyl complexes of Re(I) and Ru(II) such as [(CO)[sub 3](bpy)Re-CN-Re(bpy)(CO)[sub 3]][sup +], [(CO)[sub 3](bpy)Re-NC-Ru(bpy)[sub 2]-CN-Re(bpy)(CO)[sub 3]][sup 2+], and [(CO)[sub 3](bpy)Re-CN-Ru(dcbpy)[sub 2]-NC-Re(bpy)(CO)[sub 3]][sup 2+] (bpy = 2,2[prime]-bipyridine and dcbpy = 4,4[prime]-dicarboxy-2,2[prime]-bipyridine) have been synthesized. Their spectroscopic, redox, and photophysical properties are reported. The lowest energy CT excited state in these complexes (Re-bpy or Ru-bpy CT) is emissive in fluid solutions. In the trinuclear complexes, intense absorption in the infrared region corresponding to intervalence (IT) transitions are reported in the CT excited state and partially oxidized species. Luminescence and redox properties have been used to assess intramolecular energy/electron-transfer processes between the terminal Re(I)-polypyridyl and central Ru(II)-polypyridyl units. The intervalence transitions and the excitation spectra for the Ru-based emission suggest efficient occurrence of energy transfer from the CT excited state of the Re-based chromophore to the Ru-based unit in both complexes [(CO)[sub 3](bpy)Re-NC-Ru(bpy)[sub 2]-CN-Re(bpy)(CO)[sub 3]][sup 2+] and [(CO)[sub 3](bpy)Re-CN-Ru(dcbpy)[sub 2]-NC-Re(bpy)(CO)[sub 3]][sup 2+]. A comparison is made between the N- and C-bonded isomers and also between Re-Ru-Re- and Ru-Ru-Ru-polypyridyl trinuclear complexes.

Authors:
; ;  [1]
  1. (Institut de Chimie Physique, Lausanne (Switzerland))
Publication Date:
OSTI Identifier:
6836842
Alternate Identifier(s):
OSTI ID: 6836842
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 31:25; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; RHENIUM COMPLEXES; CHEMICAL PREPARATION; LUMINESCENCE; RUTHENIUM COMPLEXES; ABSORPTION SPECTROSCOPY; ELECTRON TRANSFER; EMISSION SPECTRA; ENERGY TRANSFER; EXCITED STATES; ISOMERIZATION; LIGANDS; PHOTOLUMINESCENCE; PYRIDINES; REDOX POTENTIAL; SPECTROSCOPY; STABILITY; AZINES; CHEMICAL REACTIONS; COMPLEXES; ENERGY LEVELS; HETEROCYCLIC COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; SPECTRA; SYNTHESIS; TRANSITION ELEMENT COMPLEXES 400201* -- Chemical & Physicochemical Properties

Citation Formats

Kalyanasundaram, K., Graetzel, M., and Nazeeruddin, M.K. Luminescence and intramolecular energy-transfer processes in isomeric cyano-bridged Rhenium(I)-Rhenium(I) and Rhenium(I)-Ruthenium(II)-Rhenium(I) polypyridyl complexes. United States: N. p., 1992. Web. doi:10.1021/ic00051a016.
Kalyanasundaram, K., Graetzel, M., & Nazeeruddin, M.K. Luminescence and intramolecular energy-transfer processes in isomeric cyano-bridged Rhenium(I)-Rhenium(I) and Rhenium(I)-Ruthenium(II)-Rhenium(I) polypyridyl complexes. United States. doi:10.1021/ic00051a016.
Kalyanasundaram, K., Graetzel, M., and Nazeeruddin, M.K. Wed . "Luminescence and intramolecular energy-transfer processes in isomeric cyano-bridged Rhenium(I)-Rhenium(I) and Rhenium(I)-Ruthenium(II)-Rhenium(I) polypyridyl complexes". United States. doi:10.1021/ic00051a016.
@article{osti_6836842,
title = {Luminescence and intramolecular energy-transfer processes in isomeric cyano-bridged Rhenium(I)-Rhenium(I) and Rhenium(I)-Ruthenium(II)-Rhenium(I) polypyridyl complexes},
author = {Kalyanasundaram, K. and Graetzel, M. and Nazeeruddin, M.K.},
abstractNote = {Mixed-metal and homometal cyano-bridged polypyridyl complexes of Re(I) and Ru(II) such as [(CO)[sub 3](bpy)Re-CN-Re(bpy)(CO)[sub 3]][sup +], [(CO)[sub 3](bpy)Re-NC-Ru(bpy)[sub 2]-CN-Re(bpy)(CO)[sub 3]][sup 2+], and [(CO)[sub 3](bpy)Re-CN-Ru(dcbpy)[sub 2]-NC-Re(bpy)(CO)[sub 3]][sup 2+] (bpy = 2,2[prime]-bipyridine and dcbpy = 4,4[prime]-dicarboxy-2,2[prime]-bipyridine) have been synthesized. Their spectroscopic, redox, and photophysical properties are reported. The lowest energy CT excited state in these complexes (Re-bpy or Ru-bpy CT) is emissive in fluid solutions. In the trinuclear complexes, intense absorption in the infrared region corresponding to intervalence (IT) transitions are reported in the CT excited state and partially oxidized species. Luminescence and redox properties have been used to assess intramolecular energy/electron-transfer processes between the terminal Re(I)-polypyridyl and central Ru(II)-polypyridyl units. The intervalence transitions and the excitation spectra for the Ru-based emission suggest efficient occurrence of energy transfer from the CT excited state of the Re-based chromophore to the Ru-based unit in both complexes [(CO)[sub 3](bpy)Re-NC-Ru(bpy)[sub 2]-CN-Re(bpy)(CO)[sub 3]][sup 2+] and [(CO)[sub 3](bpy)Re-CN-Ru(dcbpy)[sub 2]-NC-Re(bpy)(CO)[sub 3]][sup 2+]. A comparison is made between the N- and C-bonded isomers and also between Re-Ru-Re- and Ru-Ru-Ru-polypyridyl trinuclear complexes.},
doi = {10.1021/ic00051a016},
journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 31:25,
place = {United States},
year = {1992},
month = {12}
}