Journal
DALTON TRANSACTIONS
Volume 42, Issue 19, Pages 6989-7001Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3dt50266j
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Funding
- Japan Science and Technology Agency, PRESTO (Precursory Research for Embryonic Science and Technology)
- Naito Foundation
- JSPS KAKENHI [24550071]
- JSPS
- Hayashi Memorial Foundation for Female Natural Scientists
- Grants-in-Aid for Scientific Research [24550071, 12J09686] Funding Source: KAKEN
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A series of novel bichromophoric Ru(II) complexes bearing a naphthyl chromophore linked with 2,2'-bipyridyl (bpy) and 2,2'-bipyrimidine (bpm) ligands were synthesized. Complexation with a Pd-alkyl unit led to the formation of bichromophoric Ru-Pd catalysts. The photochemical and electrochemical properties of the newly synthesized compounds were studied. It has been shown that the UV-light energy absorbed at the pendant naphthyl moiety is effectively transferred to the Ru(II) center; this is supported by the observation of metal-to-ligand charge-transfer luminescence through excitation of the naphthyl unit, which is identical to the luminescence observed through visible light excitation. The luminescence lifetime of the complex bearing a naphthyl moiety directly connected to the bpy ligands was lengthened to ca. 1000 ns. When a Pd complex containing the bichromophoric unit with an extended lifetime was used as a catalyst, styrene polymerization under visible or UV light irradiation was observed, in clear contrast to dimerization using other catalysts. These results indicate the formation of an excited-state with a prolonged excited-state lifetime, which promotes an insertion step in preference to the competing beta-H elimination step.
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