journal article

Journal Article

Text

Journal of Inorganic Biochemistry. 2026, 282, p. 113344

Design, synthesis and photocatalytic activities of functionalized Re(I) bipyridine tricarbonyl complexes toward CO₂ reduction and carboxylation

Elsevier Inc.

English

Text

2026-05-12

https://doi.org/10.1016/j.jinorgbio.2026.113344

Lorwongkamol P., Saga Y., Kambe T., et al. Design, synthesis and photocatalytic activities of functionalized Re(I) bipyridine tricarbonyl complexes toward CO₂ reduction and carboxylation. Journal of Inorganic Biochemistry 282, 113344 (2026); https://doi.org/10.1016/j.jinorgbio.2026.113344.

Natural metalloenzymes efficiently catalyze chemical transformations by precisely controlling the local environment around the active site, thereby enabling selective substrate activation and reaction control. This general concept has motivated extensive efforts to improve molecular catalysts by ligand modification and functionalization. In this work, we designed and synthesized functionalized derivatives of the fac-Re(2,2′-bipyridine)(CO)₃Cl complex (Re-1), which has long been recognized as a benchmark catalyst for photochemical CO₂ reduction, and which we have recently demonstrated to also catalyze the carboxylation of organic substrates with CO₂. Using these complexes, we investigated how substituents on the bipyridine ligand affect photocatalytic activities in both CO₂ reduction and carboxylation reactions. All new complexes were fully characterized by single-crystal X-ray diffraction analysis as well as by spectroscopic and electrochemical methods. The introduction of electron-withdrawing functional groups induces clear changes in the electronic structures of the complexes, as evidenced by redshifts in their absorption spectra, CO stretching frequencies, and reduction potentials. In photocatalytic CO₂ reduction, the catalytic activities of the functionalized complexes depend strongly on these electronic properties, whereas in carboxylation reactions, all complexes show comparable catalytic performance regardless of the nature of the functional groups. Moreover, the present system also exhibits additional reactivities, including [2 + 2] dimerization and hydroacylation reactions. Collectively, this work reports the design, synthesis, and characterization of a new series of functionalized Re(I) complexes, and provides a useful experimental basis for understanding how ligand modification influences their properties and reactivity, thereby offering guidance for future development of Re-based molecular systems for CO₂ utilization.

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105154

Design, synthesis and photocatalytic activities of functionalized Re(I) bipyridine tricarbonyl complexes toward CO₂ reduction and carboxylation

Elsevier Inc.

English

2026-05-12

Journal of Inorganic Biochemistry

282

113344

https://doi.org/10.1016/j.jinorgbio.2026.113344

https://hdl.handle.net/11094/105154