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Indexed by:期刊论文

Date of Publication:2011-11-21

Journal:INORGANIC CHEMISTRY

Included Journals:PubMed、Scopus、SCIE

Volume:50

Issue:22

Page Number:11446-11460

ISSN No.:0020-1669

Abstract:[(CNPt)-N-Lambda(acac)] ((CN)-N-Lambda = cyclometalating ligand; acac = acetylacetonato) complexes in which the naphthalimide (NI) moiety is directly cyclometalated (NI as the C donor of the C-Pt bond) were synthesized. With 4-pyrazolylnaphthalimide, isomers with five-membered (Pt-2) and six-membered (Pt-3) chelate rings were obtained. With 4-pyridinylnaphthalimide, only the complex with a five-membered chelate ring (Pt-4) was isolated. A model complex with 1-phenylpyrazole as the (CN)-N-Lambda ligand was prepared (Pt-1). Strong absorption of visible light (epsilon = 21 900 M-1 cm(-1) at 443 nm for Pt-3) and room temperature (RT) phosphorescence at 630 nm (Pt-2 and Pt-3) or 674 nm (Pt-4) were observed. Long-lived phosphorescences were observed for Pt-2 (tau(p) = 12.8 mu s) and Pt-3 (tau(p) = 61.9 mu s). Pt-1 is nonphosphorescent at RT in solution because of the acac-localized T-1 excited state [based on density functional theory (DFT) calculations and spin density analysis], but a structured emission band centered at 415 nm was observed at 77 K. Time-resolved transient absorption spectra and spin density analysis indicated a NI-localized intraligand triplet excited state ((IL)-I-3) for complexes Pt-2, Pt-3, and Pt-4. DFT calculations on the transient absorption spectra (T-1 -> T-n transitions, n > 1) also support the (IL)-I-3 assignment of the T-1 excited states of Pt-2, Pt-3, and Pt-4. The complexes were used as triplet sensitizers for triplet-triplet-annihilation (TTA) based upconversion, and the results show that Pt-3 is an efficient sensitizer with an upconversion quantum yield of up to 14.1%, despite its low phosphorescence quantum yield of 5.2%. Thus, we propose that the sensitizer molecules at the triplet excited state that are otherwise nonphosphorescent were involved in the TTA upconversion process, indicating that weakly phosphorescent or nonphosphorescent transition-metal complexes can be used as triplet sensitizers for TTA upconversion.