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rdf:type
lifeskim:mentions
pubmed:issue
5
pubmed:dateCreated
2011-4-14
pubmed:abstractText
We report the redox, absorption, and emission characteristics of the tris(1,10-phenanthroline)ruthenium(II) complexes [Ru(phen)(3)](2+) bearing a (dimesityl)boryldurylethynyl (DBDE) charge-transfer (CT) unit at the 4 (4BRu(2+)) or 5 (5BRu(2+)) position of one of the three phen ligands. In acetonitrile at 298 K, 4BRu(2+) showed absorption and emission maximum wavelengths at 473 and 681 nm, respectively, which were shifted to longer wavelengths by 25 and 74 nm, respectively, compared with the relevant value of 5BRu(2+), 448 and 607 nm, respectively. The effects of a fluoride ion on the absorption and emission spectra of the complexes demonstrated that the CT interaction between the ?-electron system in the phen ligand (?(aryl)) and the vacant p orbital on the boron atom (p(B)) in the DBDE group (i.e., ?(aryl)-p(B) CT) participated in the excited states of the complexes in addition to the Ru(II)-to-phen metal-to-ligand CT (MLCT) interaction. Reflecting such synergistic MLCT/?(aryl)-p(B) CT, both 4BRu(2+) and 5BRu(2+) exhibited intense emission at 298 K with a quantum yield of 0.11. Furthermore, the emission lifetime of 4BRu(2+) was as long as 12 ?s and almost independent of the temperature (T = 280-330 K). The present study indicated that the nonemissive dd excited triplet state did not participate to nonradiative decay in the MLCT excited triplet state of 4BRu(2+). The effects of the synergistic MLCT/?(aryl)-p(B) CT interactions on the redox, absorption/emission, and photophysical characteristics of 4BRu(2+) and 5BRu(2+) are discussed in detail.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Mar
pubmed:issn
1520-510X
pubmed:author
pubmed:copyrightInfo
© 2011 American Chemical Society
pubmed:issnType
Electronic
pubmed:day
7
pubmed:volume
50
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
1603-13
pubmed:year
2011
pubmed:articleTitle
Long-lived and temperature-independent emission from a novel ruthenium(II) complex having an arylborane charge-transfer unit.
pubmed:affiliation
Department of Chemistry, Faculty of Science, Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan. sakueri@sci.hokudai.ac.jp
pubmed:publicationType
Journal Article