ic6b00437_si_002.cif (127.8 kB)
Dinuclear Ruthenium Complex Based on a π‑Extended Bridging Ligand with Redox-Active Tetrathiafulvalene and 1,10-Phenanthroline Units
dataset
posted on 2016-04-12, 15:53 authored by Bin Chen, Zhong-Peng Lv, Carol Hua, Chanel F. Leong, Floriana Tuna, Deanna M. D’Alessandro, David Collison, Jing-Lin ZuoThe synthesis of
a π-extended bridging ligand with both redox-active tetrathiafulvalene
(TTF) and 1,10-phenanthroline (phen) units, namely, bis(1,10-phenanthro[5,6-b])tetrathiafulvalene (BPTTF), was realized via a self-coupling
reaction. Using this ligand and Ru(tbbpy)2Cl2 (tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine),
the dinuclear ruthenium(II) compound [{Ru(tbbpy)2}2(BPTTF)](PF6)4 (1) has
been obtained by microwave-assisted synthesis. Structural characterization
of 1 revealed a crossed arrangement of the TTF moieties
on adjacent dimers within the crystal structure. The optical and redox
properties of 1 were investigated using electrochemical,
spectroelectrochemical, electron paramagnetic resonance (EPR), and
absorption spectroscopic studies combined with theoretical calculations.
One exhibits a rich electrochemical behavior owing to the multiple
redox-active centers. Interestingly, both the ligand BPTTF and the
ruthenium compound 1 are EPR-active in the solid state
owing to intramolecular charge-transfer processes. The results demonstrate
that the TTF-annulated bis(phen) ligand is a promising bridging ligand
to construct oligomeric or polymeric metal complexes with multiple
redox-active centers.