%0 Journal Article %1 Patra.2005b %A Patra, Srikanta %A Sarkar, Biprajit %A Maji, Somnath %A Fiedler, Jan %A Urbanos, Francisco A. %A Jimenez-Aparicio, Reyes %A Kaim, Wolfgang %A Lahiri, Goutam Kumar %D 2005 %J Chemistry - A European Journal %K imported %N 2 %P 489--498 %T Controlling metal-ligand-metal oxidation state combinations by ancillary ligand (L) variation in the redox systems L2Ru(mu-boptz)RuL2n, boptz = 3,6-bis(2-oxidophenyl)-1,2,4,5-tetrazine, and L = acetylacetonate, 2,2'-bipyridine, or 2-phenylazopyridine %V 12 %X The new compounds (acac)2Ru(mu-boptz)Ru(acac)2 (1), (bpy)2Ru(mu-boptz)Ru(bpy)2(ClO4)2 (2-(ClO4)2), and (pap)2Ru(mu-boptz)Ru(pap)2(ClO4)2 (3-(ClO4)2) were obtained from 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine (H2boptz), the crystal structure analysis of which is reported. Compound 1 contains two antiferromagnetically coupled (J = -36.7 cm(-1)) Ru(III) centers. We have investigated the role of both the donor and acceptor functions containing the boptz2- bridging ligand in combination with the electronically different ancillary ligands (donating acac-, moderately pi-accepting bpy, and strongly pi-accepting pap; acac = acetylacetonate, bpy = 2,2'-bipyridine pap = 2-phenylazopyridine) by using cyclic voltammetry, spectroelectrochemistry and electron paramagnetic resonance (EPR) spectroscopy for several in situ accessible redox states. We found that metal-ligand-metal oxidation state combinations remain invariant to ancillary ligand change in some instances; however, three isoelectronic paramagnetic cores Ru(mu-boptz)Ru showed remarkable differences. The excellent tolerance of the bpy co-ligand for both Ru(III) and Ru(II) is demonstrated by the adoption of the mixed-valent form in L2Ru(mu-boptz)RuL23+, L = bpy, whereas the corresponding system with pap stabilizes the Ru(II) states to yield a phenoxyl radical ligand and the compound with L = acac- contains two Ru(III) centers connected by a tetrazine radical-anion bridge.on SciFinder (R)

@article{Patra.2005b, abstract = {The new compounds [(acac)2Ru(mu-boptz)Ru(acac)2] (1), [(bpy)2Ru(mu-boptz)Ru(bpy)2](ClO4)2 (2-(ClO4)2), and [(pap)2Ru(mu-boptz)Ru(pap)2](ClO4)2 (3-(ClO4)2) were obtained from 3,6-bis(2-hydroxyphenyl)-1,2,4,5-tetrazine (H2boptz), the crystal structure analysis of which is reported. Compound 1 contains two antiferromagnetically coupled (J = -36.7 cm(-1)) Ru(III) centers. We have investigated the role of both the donor and acceptor functions containing the boptz2- bridging ligand in combination with the electronically different ancillary ligands (donating acac-, moderately pi-accepting bpy, and strongly pi-accepting pap; acac = acetylacetonate, bpy = 2,2'-bipyridine pap = 2-phenylazopyridine) by using cyclic voltammetry, spectroelectrochemistry and electron paramagnetic resonance (EPR) spectroscopy for several in situ accessible redox states. We found that metal-ligand-metal oxidation state combinations remain invariant to ancillary ligand change in some instances; however, three isoelectronic paramagnetic cores Ru(mu-boptz)Ru showed remarkable differences. The excellent tolerance of the bpy co-ligand for both Ru(III) and Ru(II) is demonstrated by the adoption of the mixed-valent form in [L2Ru(mu-boptz)RuL2]3+, L = bpy, whereas the corresponding system with pap stabilizes the Ru(II) states to yield a phenoxyl radical ligand and the compound with L = acac- contains two Ru(III) centers connected by a tetrazine radical-anion bridge.[on SciFinder (R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Patra, Srikanta and Sarkar, Biprajit and Maji, Somnath and Fiedler, Jan and Urbanos, Francisco A. and Jimenez-Aparicio, Reyes and Kaim, Wolfgang and Lahiri, Goutam Kumar}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/226283bdf1476e51ab91b30068f65c3aa/huebleriac}, interhash = {e8bff8e55e9e805808f360ff3f5450be}, intrahash = {26283bdf1476e51ab91b30068f65c3aa}, issn = {0947-6539}, journal = {Chemistry - A European Journal}, keywords = {imported}, number = 2, pages = {489--498}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Controlling metal-ligand-metal oxidation state combinations by ancillary ligand (L) variation in the redox systems [L2Ru(mu-boptz)RuL2]n, boptz = 3,6-bis(2-oxidophenyl)-1,2,4,5-tetrazine, and L = acetylacetonate, 2,2'-bipyridine, or 2-phenylazopyridine}, volume = 12, year = 2005 }