The isomeric title complexes Ru(trpy)(L)Cl+ were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl3 and 3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (L). Crystal structure analyses of the perchlorate hemihydrates, electrochem. and spectroscopic (NMR, UV/visible, EPR) studies, supported by DFT calcns., reveal distinct differences between the isomeric redox series 1n+ (tetrazine-Nt trans to Cl) and 2n+ (pyrazolyl-Np trans to Cl; n = 0, 1, 2). The latter system with the p acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidn., lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidized (RuIII) state. According to partially resolved EPR spectra of 1-electron reduced neutral compds. 1 and 2, they have the unpaired electron predominantly in the tetrazine ring of L. on SciFinder(R)
%0 Journal Article
%1 Patra.2005
%A Patra, Srikanta
%A Sarkar, Biprajit
%A Ghumaan, Sandeep
%A Patil, Mahendra P.
%A Mobin, Shaikh M.
%A Sunoj, Raghavan B.
%A Kaim, Wolfgang
%A Lahiri, Goutam Kumar.
%D 2005
%J Dalton Transactions
%K crystal isomer isomer;DFT isomer;electrochem isomer;ruthenium prepn;UV pyrazolyltetrazine ruthenium spectroelectrochem structure terpyridine visible
%N 7
%P 1188--1194
%R 10.1039/b500152h
%T Isomeric ruthenium terpyridine complexes Ru(trpy)(L)Cln+ containing the unsymmetrically bidentate acceptor L = 3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine. Synthesis, structures, electrochemistry, spectroscopy and DFT calculations
%X The isomeric title complexes Ru(trpy)(L)Cl+ were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl3 and 3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (L). Crystal structure analyses of the perchlorate hemihydrates, electrochem. and spectroscopic (NMR, UV/visible, EPR) studies, supported by DFT calcns., reveal distinct differences between the isomeric redox series 1n+ (tetrazine-Nt trans to Cl) and 2n+ (pyrazolyl-Np trans to Cl; n = 0, 1, 2). The latter system with the p acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidn., lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidized (RuIII) state. According to partially resolved EPR spectra of 1-electron reduced neutral compds. 1 and 2, they have the unpaired electron predominantly in the tetrazine ring of L. on SciFinder(R)
@article{Patra.2005,
abstract = {The isomeric title complexes [Ru(trpy)(L)Cl]+ were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl3 and 3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (L). Crystal structure analyses of the perchlorate hemihydrates, electrochem. and spectroscopic (NMR, UV/visible, EPR) studies, supported by DFT calcns., reveal distinct differences between the isomeric redox series [1]n+ (tetrazine-Nt trans to Cl) and [2]n+ (pyrazolyl-Np trans to Cl; n = 0, 1, 2). The latter system with the \textgreek{p} acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidn., lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidized (RuIII) state. According to partially resolved EPR spectra of 1-electron reduced neutral compds. 1 and 2, they have the unpaired electron predominantly in the tetrazine ring of L. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Patra, Srikanta and Sarkar, Biprajit and Ghumaan, Sandeep and Patil, Mahendra P. and Mobin, Shaikh M. and Sunoj, Raghavan B. and Kaim, Wolfgang and Lahiri, Goutam Kumar.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/238722eecdd4cc396d512939ae59bca36/b_schwederski},
doi = {10.1039/b500152h},
interhash = {7cebe4c60e8285565678c0f88e6f88c7},
intrahash = {38722eecdd4cc396d512939ae59bca36},
issn = {1477-9226},
journal = {Dalton Transactions},
keywords = {crystal isomer isomer;DFT isomer;electrochem isomer;ruthenium prepn;UV pyrazolyltetrazine ruthenium spectroelectrochem structure terpyridine visible},
number = 7,
pages = {1188--1194},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Isomeric ruthenium terpyridine complexes [Ru(trpy)(L)Cl]n+ containing the unsymmetrically bidentate acceptor L = 3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine. Synthesis, structures, electrochemistry, spectroscopy and DFT calculations},
year = 2005
}