%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 = {2022-06-15T11:26:56.000+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/huebleriac}, 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 = {2022-06-15T09:26:56.000+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 }