The fac-[Re(CO) 3 (deeb)L] + complex (C2) where L is the (E)-2-((3-amino-pyridin-4-ylimino)-methyl)-4,6di-tert-butylphenol ancillary ligand, which presents an intramolecular hydrogen bond, has been synthesized and characterized using UV-vis, 1 H-NMR, FT-IR, cyclic voltammetry and DFT calculations.The UV-vis absorption and emission properties have been studied at room temperature and the results were compared with TDDFT calculations including spin-orbit effects. We report an alternative synthesis route for the fac-Re(CO) 3 (deeb)Br (C1) complex where deeb = (4,4 0 -diethanoate)-2,2 0 -bpy. Besides, wehave found that the C1 shows a red shift in the emission spectrum due to the nature of the ancillary electron donating ligand, while the C2 complex shows a blue shift in the emission spectrum suggesting that the ancillary ligand L has electron withdrawing ability and the importance of the intramolecular hydrogen bond. The calculations suggest that an experimental mixed absorption band at 361 nm could be assigned to MLCT and LLCT transitions. The electron withdrawing nature of the ancillary ligand in C2 explains the electrochemical behavior, which shows the oxidation of Re I at 1.83 V and the reduction of deeb at À0.77 V. 1.44 [s, 6H, (-CH 3 )], 4.49 [m, 4H], 5.92 [s, 2H, -NH 2 ], 6.45 [d; J = 5.5 Hz; 1H], 7.28 [d; J = 1.5 Hz; 1H], 7.47 [s, 1H], 7.51 [s, 1H], 7.53 [s, 1H], 8.11 [s, 1H], 8.20 [d; J = 5.5 Hz; 2H], 8.91 [s, 2H], Scheme 1 Structures of deeb and L ligands used in this work.

We have prepared a new monometallic rhenium(I) carbonyl, the complex [P,N-{(C 6 H 5 ) 2 (C 5 H 5 N)P}Re(CO) 3 Br] by direct reaction of (Re(CO) 3 Br(THF)) 2 and the ligand (C 6 H 5 ) 2 (C 5 H 5 N)P The structure in the complex shows the pyridinic-phosphine ligand in a chelating mode, occupying cis positions around the rhenium octahedral environment. The molecule displays an absorption band centered at 315 nm which has been assigned to a MLCT transition, and a luminescence quantum yield of 0.001.

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Artículo de publicación ISIRhenium complexes are versatile molecular building blocks whose tunable photophysical properties are useful in diverse opto-related applications. Herein we report the synthesis and characterization of a novel ReI tricarbonyldiimine complex, [(phen)Re(CO)3Br] (phen: 1,10-phenanthroline), which was found to be an efficient singlet oxygen [O2(1Δg)] photosensitizer in homogeneous solution [ΦO2(1Δg) = 0.55 (dichloromethane) and 0.16 (dimethylformamide)]. The photophysical properties of [(phen)Re(CO)3Br] were thoroughly characterized in solution and modeled by means of density functional theory (DFT) and time-dependent (TD)-DFT quantum mechanical calculations. The Re complex was incorporated into a flexible polymeric silsesquioxane (SSO) film, which has excellent dopant compatibility, chemical resistance, and mechanical properties. When [(phen)Re(CO)3Br] is embedded in the SSO film, it is found to retain most of the photophysical characteristics observed for the complex in solution. In particular, the [(phen)Re(CO)3Br]-doped SSO films were able to photosensitize O2(1Δg) when illuminated with blue light (∼405 nm). The O2(1Δg) sensitization by films in acetonitrile was followed by the photooxidation of the well-known O2(1Δg) chemical trap 9,10-dimethylanthracene (DMA) and confirmed by the direct observation of the O2(1Δg) luminescence spectrum (centered at 1270 nm) and the measurement of its kinetic profile. These results highlight the potential application of this type of polymeric material in the production of biological- or microbial-photoinactivating flexible surfaces or in the implementation of interfacial solid/liquid strategies for the photoinduced oxidation of organic compounds in solution.CONICYT 7913003