Sarantou, A.; Tsipis, A. Photocatalytic Reduction of CO2 into CO with Cyclometalated Pt(II) Complexes of N^C^N Pincer Dipyridylbenzene Ligands: A DFT Study. Molecules2024, 29, 403.
Sarantou, A.; Tsipis, A. Photocatalytic Reduction of CO2 into CO with Cyclometalated Pt(II) Complexes of N^C^N Pincer Dipyridylbenzene Ligands: A DFT Study. Molecules 2024, 29, 403.
Sarantou, A.; Tsipis, A. Photocatalytic Reduction of CO2 into CO with Cyclometalated Pt(II) Complexes of N^C^N Pincer Dipyridylbenzene Ligands: A DFT Study. Molecules2024, 29, 403.
Sarantou, A.; Tsipis, A. Photocatalytic Reduction of CO2 into CO with Cyclometalated Pt(II) Complexes of N^C^N Pincer Dipyridylbenzene Ligands: A DFT Study. Molecules 2024, 29, 403.
Abstract
In this work, Density Functional Theory (DFT) calculations were employed to study the photocatalytic CO2 to CO reduction by a series of Pt(II) square planar complexes with general formula [Pt(5-R-dpb)Cl] (dpb = 1,3-di(2-pyridyl)benzene anion, R = H, N,N-dimethylaniline,T thiophene, diazaborinine). The CO2 to CO conversion process is thought to proceed via two main steps, namely the photocatalytic/reduction step and the main catalytic step. The simulated absorption spectra exhibit strong bands in the 200 – 400 nm UV-Vis region. The calculated excited state reduction potentials are in the range 0.32 — -0.36 V revealing that the reductive quenching of the T1 state of the complexes could be modulated with suitable changes of the N^C^N pincer ligands. The CO2 fixation and activation by the ‘real’ three coordinated Pt(II) catalyst/intermediate is predicted to be favorable with Pt-CO2 bond dissociation energies, D0 in the range -36.9—-10.3 kcal/mol. The nature of the Pt-CO2 bond is complex with covalent, hyperconjugative and H-bonding interactions prevailing the repulsive electrostatic interactions. The main catalytic cycle is estimated to be a favorable exergonic process.
Keywords
Photocatalytic CO2 reduction; DFT/TDDFT; Pt(II) pincer complexes; T1 excited state electrochemistry, CO2 fixation/activation by Pt
Subject
Chemistry and Materials Science, Theoretical Chemistry
Copyright:
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