trans-cis Photoisomerization of the styrylpyridine Ligand in [Re(CO)3(2,2'-bipyridine)(t-4-styrylpyridine)]+: role of the metal-to-ligand charge-transfer excited states

Chemistry : a European Journal
Julien Bossert, Chantal Daniel

Abstract

The trans-cis isomerization of the styrylpyridine carbon-carbon double bond induced by visible light irradiation in fac-[Re(CO)(3)(bpy)(stpy)](+) (bpy = 2,2'-bipyridine; stpy = t-4-styrylpyridine) has been investigated by means of quantum-chemical methods. The structures of the various cis and trans conformers of [Re(CO)(3)(bpy)(stpy)](+) have been optimized at the density functional theory (DFT) level. Three rotational conformers for the most stable trans isomer lie within 2.3 kJ mol(-1) each other. The energy difference between the cis and trans isomers is 27.0 kJ mol(-1). The electronic spectroscopy of the most stable conformers has been investigated by time-dependent DFT (TD-DFT) and complete active space self-consistent field/CAS second order perturbation theory (CASSCF/CASPT2) calculations. The lowest absorption bands are dominated by metal-to-ligand charge-transfer (MLCT, d(Re)-->pi*(bpy)) transitions calculated at about 25,000 cm(-1) and by a strong intraligand (1)IL (pi(stpy)-->pi*(stpy)) transition in the near UV region. On the basis of CASSCF potential energy curves (PECs) calculated as a function of the torsion angle of the C=C bond of the styrylpyridine ligand, it is shown that the role of the low-lying MLCT states...Continue Reading

References

Jun 7, 2000·Chemistry : a European Journal·I R FarrellA Vlcek
Jul 3, 2003·Journal of the American Chemical Society·Thomas SchultzAlbert Stolow
Mar 12, 2004·Journal of the American Chemical Society·Alessandro CembranGiorgio Orlandi
Apr 28, 2004·Chemistry : a European Journal·Cosimo CiminelliMaurizio Persico

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Citations

Apr 15, 2014·Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy·Ezequiel Wolcan
Jan 27, 2012·Bioorganic & Medicinal Chemistry Letters·Robert N HansonRichard B Hochberg
Jul 21, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Kassio P S Zanoni, Neyde Y Murakami Iha
Sep 1, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Ronaldo C Amaral, Neyde Y Murakami Iha
Sep 30, 2010·Chemical Communications : Chem Comm·Etienne GindenspergerChantal Daniel
Apr 22, 2011·Chemical Communications : Chem Comm·Ju-Ling LinAlistair J Lees
Sep 27, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Megumi KayanumaChantal Daniel
May 9, 2013·Inorganic Chemistry·Antonio Otavio T PatrocinioNeyde Y Murakami Iha
Jun 29, 2018·The Journal of Physical Chemistry. a·Ronaldo C AmaralNeyde Y Murakami Iha
Aug 28, 2021·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Shruti MukherjeeSujoy Baitalik
Oct 31, 2008·Inorganic Chemistry·Antonio Otávio T Patrocínio, Neyde Y Murakami Iha
Oct 19, 2007·The Journal of Physical Chemistry. a·Marie-France Charlot, Ally Aukauloo

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