This paper describes the physicochemical properties of a rhenium (Re) complex [Re(bpy)(CO)₃Cl] immobilized on a bipyridine‐periodic mesoporous organosilica (BPy‐PMO) acting as a solid support. The immobilized Re complex generated a metal‐to‐ligand charge transfer absorption band at 400 nm. This wavelength is longer than that exhibited by Re(bpy)(CO)₃Cl in the polar solvent acetonitrile (371 nm) and is almost equal to that in nonpolar toluene (403 nm). The photocatalytic activity of this heterogeneous Re complex was lower than that of a homogeneous Re complex due to the reduced phosphorescence lifetime resulting from immobilization. However, the catalytic activity was enhanced by the co‐immobilization of the ruthenium (Ru) photosensitizer [Ru(bpy)₃]²⁺ on the PMO pore surfaces. Quantum chemical calculations suggest that electron transfer between the Ru and Re complexes occurs through interactions between the molecular orbitals in the pore walls. These results should have applications to the design of efficient heterogeneous CO₂ reduction photocatalysis systems.

中文翻译：

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Re（bpy）（CO）3Cl固定在联吡啶-周期性介孔有机硅上，用于光催化还原CO2

本文描述了固定在联吡啶周期介孔有机硅（BPy-PMO）上的a （Re）络合物[Re（bpy）（CO）₃ Cl]的物理化学性质。固定化的Re复合物在400 nm处产生了一个金属到配体的电荷转移吸收带。该波长长于极性溶剂乙腈中的Re（bpy）（CO）₃ Cl波长（371 nm），几乎等于非极性甲苯中的波长（403 nm）。由于固定化导致的磷光寿命缩短，该异质Re配合物的光催化活性低于均质Re配合物。然而，钌（Ru）光敏剂[Ru（bpy）₃ ]的共固定化增强了催化活性。PMO孔表面的²⁺。量子化学计算表明，Ru和Re配合物之间的电子转移是通过孔壁中分子轨道之间的相互作用而发生的。这些结果应可用于设计高效的异质CO ₂还原光催化系统。