Syntheses and electronic and optical properties of complexes of the bis(2,2′-bipyrazyl)ruthenium unit

• Published in: Polyhedron 2015-08, Vol.96, p.57-65
• Main Authors: Coe, Benjamin J., Peers, Martyn K., Scrutton, Nigel S.
• Format: Article
• Language: English
• Subjects: 2,2′-Bipyrazyl; Density functional theory; Electrochemistry; Ruthenium complexes; UV–Vis spectroscopy
• ISSN: 0277-5387
• DOI: 10.1016/j.poly.2015.04.028

New complexes cis-[RuII(bpz)2(L–L)]n+ (bpz=2,2′-bipyrazyl, n=2 or 4, L–L=a 4,4′-disubstituted 2,2′-bipyridyl derivative) have been prepared and studied by using techniques including UV–Vis spectroscopy, cyclic voltammetry and TD-DFT calculations. Their photoredox properties are highly tunable, with the bpz ligands acting as stronger electron acceptors than any of the L–L ligands (even the –CF3 derivative). [Display omitted] Seven new complexes of the form cis-[RuII(bpz)2(L–L)]n+ (bpz=2,2′-bipyrazyl: n=2; L–L=4,4′-bis(tert-butyl)-2,2′-bipyridyl, 4,4′-diphenyl-2,2′-bipyridyl, 4,4′-dichloro-2,2′-bipyridyl, 4,4′-diamino-2,2′-bipyridyl, 4,4′-bis(trifluoromethyl)-2,2′-bipyridyl, 4,4′-bis(methoxycarbonyl)-2,2′-bipyridyl: n=4; L–L=N″,N′″-dimethyl-4,4′:2′,2″:4″,4′″-quaterpyridinium) are prepared and isolated as their PF6− and Cl− salts. Improved methods for synthesising bpz and 4,4′-bis(trifluoromethyl)-2,2′-bipyridyl are described also. Characterisation involves various techniques including 1H NMR spectroscopy and mass spectrometry. The new compounds are studied alongside the known species where n=2 and L–L=2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl or 2,2′-bipyrimidine. Their UV–Vis spectra display intense intraligand π→π∗ absorptions, and also metal-to-ligand charge-transfer (MLCT) bands with two resolved maxima in the visible region. Red-shifts in the MLCT bands occur as the electron-donating strength of L–L increases. Cyclic voltammograms show reversible RuIII/II oxidation waves, and several ligand-based reductions that are also mostly reversible. The variations in the redox potentials correlate with changes in the MLCT energies. Time-dependent density functional theory calculations give relatively good correlations with the experimental UV–Vis spectra for selected complexes when using the M06 functional and basis sets Def2-QZVP (on Ru) and Def2-SVP (on all other atoms) in acetonitrile. The lowest energy visible absorption band is confirmed to be due to RuII→bpz MLCT, while further such transitions occur along with MLCT to L–L at higher energies.