Synthesis, characterization, and electrochemistry of biorelevant photosensitive low-potential orthometalated ruthenium complexes
2005 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 44, no 5, 1626-1634 p.Article in journal (Refereed) Published
Redox potentials of photosensitive cyclometalated Ru derivatives of 2-phenylpyridine or 2-(4-tolyl)pyridine are controllably decreased by up to 0.8 V within several minutes. This is achieved by irradiation of the ruthena(II)cycles cis-[Ru(o-X-2-py)(LL)(MeCN)(2)]PF6 (2, X = C6H4 (a) or 4-MeC6H3 (b), LL = 1,10-phenanthroline or 2,2'-bipyridine). The cis geometry of the MeCN ligands has been confirmed by the X-ray structural studies. The sigma-bound sp(2) carbon of the metalated ring is trans to LL nitrogen. Complexes 2 are made from [Ru(o-X-2-py)(MeCN)(4)]PF6 (1) and I-L. This trivial ligand substitution is unusual because la reacts readily with phen in MeCN as solvent to give cis-[Ru(o-C6H4-2-py)(phen)(MeCN)(2)]PF6 (2c) in a 83% yield, but bpy does not afford the bpy-containing 2 under the same conditions. cis-[Ru(o-C6H4-2-py)(bpy)(MeCN)(2)]PF6 (2e) has been prepared in CH2Cl2 (74%). Studies of complexes 2c,e by cyclic voltammetry in MeOH in the dark reveal Ru-II/III quasy-reversible redox features at 573 and 578 mV (vs Ag/AgCl), respectively. A minute irradiation 2c and 2e converts them into now species with redox potentials of -230 and 270 mV, respectively. An exceptional potential drop for 2c is accounted for in terms of a photosubstitution of both MeCN ligands by methanol. ESR, H-1 NMR, and UV-vis data indicate that the primary product of photolysis of 2c is an octahedral monomeric low-spin (S = 112) Ru-III species, presumably cis-[Ru-II(o-C6H4-2-py)(phen)(MeOH)2]2+. The primary photoproduct of bpy complex 2e is cis-[Ru-II(O-C6H4-2-py)(bpy)(MeCN)(MeOH)](+), and this accounts for a lower decrease in the redox potential. Irradiation of 2c in the presence of added chloride affords [(phen)(o-C6H4-2-py)(ClRuORuCl)-O-III-Cl-IV(o-C6H4-2-py)(phen)]PF6, a first mu-oxo-bridged mixed valent dimer with a cyclometalated unit. The structure of the dimer has been established by X-ray crystallography.
Place, publisher, year, edition, pages
2005. Vol. 44, no 5, 1626-1634 p.
horseradish-peroxidase, photosubstitution reactions, cyclometalated complexes, redox properties, glucose-oxidase, water-oxidation, photochemistry, biomaterials, mediators, catalysis
IdentifiersURN: urn:nbn:se:kth:diva-14570DOI: 10.1021/ic048270wISI: 000227346300065ScopusID: 2-s2.0-20044376079OAI: oai:DiVA.org:kth-14570DiVA: diva2:332611
QC 201005252010-08-052010-08-05Bibliographically approved