Indexed by:期刊论文

Date of Publication:2012-06-01

Journal:CHEMISTRY-A EUROPEAN JOURNAL

Included Journals:SCIE、EI、PubMed、Scopus

Volume:18

Issue:26

Page Number:8100-8112

ISSN No.:0947-6539

Key Words:density functional calculations; iridium; naphthalimide; photochemistry; upconversion

Abstract:Cyclometalated IrIII complexes with acetylide ppy and bpy ligands were prepared (ppy=2-phenylpyridine, bpy=2,2'-bipyridine) in which naphthal (Ir-2) and naphthalimide (NI) were attached onto the ppy (Ir-3) and bpy ligands (Ir-4) through acetylide bonds. [Ir(ppy)3] (Ir-1) was also prepared as a model complex. Room-temperature phosphorescence was observed for the complexes; both neutral and cationic complexes Ir-3 and Ir-4 showed strong absorption in the visible range (e=39600?M-1?cm-1 at 402 nm and e=25100?M-1?cm-1 at 404 nm, respectively), long-lived triplet excited states (tT=9.30 mu s and 16.45 mu s) and room-temperature red emission (?em=640 nm, Fp=1.4?% and ?em=627 nm, Fp=0.3?%; cf. Ir-1: e=16600?M-1?cm-1 at 382 nm, tem=1.16 mu s, Fp=72.6?%). Ir-3 was strongly phosphorescent in non-polar solvent (i.e., toluene), but the emission was completely quenched in polar solvents (MeCN). Ir-4 gave an opposite response to the solvent polarity, that is, stronger phosphorescence in polar solvents than in non-polar solvents. Emission of Ir-1 and Ir-2 was not solvent-polarity-dependent. The T1 excited states of Ir-2, Ir-3, and Ir-4 were identified as mainly intraligand triplet excited states (3IL) by their small thermally induced Stokes shifts (?Es), nanosecond time-resolved transient difference absorption spectroscopy, and spin-density analysis. The complexes were used as triplet photosensitizers for triplet-triplet annihilation (TTA) upconversion and quantum yields of 7.1?% and 14.4?% were observed for Ir-2 and Ir-3, respectively, whereas the upconversion was negligible for Ir-1 and Ir-4. These results will be useful for designing visible-light-harvesting transition-metal complexes and for their applications as triplet photosensitizers for photocatalysis, photovoltaics, TTA upconversion, etc.