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.
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.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
authors.forename: Srikanta
authors.initials: S
authors.lastname: Patra
authors.forename: Biprajit
authors.initials: B
authors.lastname: Sarkar
authors.forename: Somnath
authors.initials: S
authors.lastname: Maji
authors.forename: Jan
authors.initials: J
authors.lastname: Fiedler
authors.forename: Francisco A
authors.initials: FA
authors.lastname: Urbanos
authors.forename: Reyes
authors.initials: R
authors.lastname: Jimenez-Aparicio
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Kaim
authors.forename: Goutam Kumar
authors.initials: GK
authors.lastname: Lahiri