Indexed by:期刊论文

Date of Publication:2014-05-21

Journal:JOURNAL OF MATERIALS CHEMISTRY B

Included Journals:SCIE、EI、Scopus

Volume:2

Issue:19

Page Number:2838-2854

ISSN No.:2050-750X

Abstract:Heteroleptic C boolean AND N cyclometalated iridium(III) complexes incorporating a monostyryl/distyryl BODIPY ligand via acetylide bonds of 2,2 '-bipyridine (bpy) with both absorption(ca.epsilon = 38.96 x 104 M-1 cm(-1), 9.89 x 10(4) M-1 cm(-1), and 7.89 x 10(4) M-1 cm(-1) at 664 nm, 644 nm, and 729 nm for Ir-2, Ir-3 and Ir-4, respectively) and fluorescence emission bands (ca. 624-794 nm for Ir-1, Ir-2, Ir-3 and Ir-4) in the near infra-red region (NIR) and exceptionally long-lived triplet excited states (tau = 156.5 mu s for Ir-2) have been reported. Ir(ppy)(3) (Ir-0; ppy 2-phenylpyridine) was used as reference, which gives the typical weak absorption in visible range (epsilon = 1.51 x 10(4) M-1 cm(-1) M-1 cm(-1) at 385 nm). The nanosecond time-resolved transient absorption and DFT calculations proposed that styryl BODIPY-localized long lived (IL)-I-3 states were populated for Ir-1, Ir-2, Ir-3 and Ir-4 (tau(T) -106.6 mu s, 156.5 mu s, 92.5 mu s and 31.4 mu s, respectively) upon photoexcitation. The complexes were used as triplet photosensitizers for singlet oxygen (O-1(2)) mediated photooxidation of 1,5dihydronaphthalene to produce juglone. The O-1(2) quantum yields (phi(Delta)) of Ir-1 (0.53) and Ir-2 (0.81) are ca. 9-fold of Ir-3 (0.06) and 40-fold of Ir-4 (0.02), respectively. Ir-2 has high molar absorption coefficient at 664 nm, moderate fluorescence in the NIR region, and high singlet oxygen quantum yield (phi(Delta) 0.81), exhibits predominate photocytotoxicity over dark cytotoxicity in LLC cells (lung cancer cells) upon irradiation, making it potentially suitable for use in in vivo photodynamic therapy (PDT). Our results are useful for preparation of transition metal complexes that show strong absorption of visible light in the NIR region with long-lived triplet excited states and for the application of these complexes in photocatalysis and theranostics such as simultaneous photodynamic therapy (PDT) and luminescent bioimaging.