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Rational design of co-ordination compounds in combination of bipyridine type of ligands and group 7 metal (M = Mn, Re) for photoCORM: a DFT study

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Abstract

Context

A large number of manganese and rhenium tricarbonyl complexes are known in literature along with various applications in different fields. CO-releasing molecules (CORMs) got recent research attention because CO can act as a prodrug for different diseases. CORMs offer the promising prospect of a safe and controllable amount of CO release. In this research work, we have explored the electronic properties of compounds such as bipyridine-related [Mn(CO)3] and [Re(CO)3] and we have compared the electronic properties of both manganese and rhenium tricarbonyl complexes in the light of carbon monoxide releasing tendency. The chosen Mn and Re metals have enough possibility to vary or play with ligands and design a new and novel CORM molecule. In this context, we have taken a range of 4,4′-disubstituted 2,2′ bipyridyl ligands (Rbpy, where R = NH2, tBu, OCH3, H, CF3, CN, NO2) to investigate CO’s liberation ability to identify and study such molecules. The calculated absorbance of designed complexes (1–14) shows visible/near-IR region (350–850 nm). The HOMO-LUMO energy gap of 7 (ΔE=2.40 eV) complex and for complex 14 (ΔE=2.28 eV) which is lesser in all complexes but the MLCT percentage is greater in Mn tricarbonyl complexes in comparison to Re tricarbonyl complexes. The calculated results of the FMO approach revealed that complex 7 and 14 have the lowest energy gap which is also in good agreement with DOSs and TDM results. The theoretically calculated results revealed that the both Mn and Re tricarbonyl complexes have a tendency for labialization of CO, but Mn tricarbonyl complexes are more prone to CO release because they have higher MLCT percentage.

Methods

In this research work, we have performed density functional theory (DFT) calculations to explore the physical properties of compounds such as bipyridine-related [Mn(CO)3] and [Re(CO)3] and we have compared the physical properties of both manganese and rhenium tricarbonyl complexes in the light of carbon monoxide releasing tendency. DFT-based calculations were performed by using B3LYP/LANL2DZ basis set followed by acetonitrile solvent using the conductor-like polarizable continuum model (CPCM) for different calculations. Various geometrical calculations were performed using the Gaussian16 suite of programs and the output results obtained from Gaussian16 were visualized using GaussView 5.0.16. The same level of theory was used for various calculations, including frontier molecular orbital (FMO) analysis, metal to ligand charge transfer (MLCT), density of state (DOS) calculations, and transition density of matrix (TDM) calculations. For specific calculations, GaussSum 2.2 software package was used to calculate the density of states, and the Multiwfn 3.8 program was used to analyze the transition density matrix, which is presented using heat maps for both electrons and holes.

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Data availability

We have used Gaussian 16, GaussSum and multiwfn 3.8 software.

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Funding

Financial support has been given by Science and Engineering Research Board (SERB) (Ref. no. CRG/2019/001032) under core research grant for design of the study and collection, analysis, interpretation of data, and in writing the manuscript.

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  1. Department of Chemistry, Prof. Rajendra Singh (Rajju Bhaiya) Institute of Physical Sciences for Study and Research, V. B. S. Purvanchal University Jaunpur, UP, Jaunpur, 222003, India

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Ritu Seth performed the study and wrote the manuscript and Ajeet Singh executed the idea of the research.

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Seth, R., Singh, A. Rational design of co-ordination compounds in combination of bipyridine type of ligands and group 7 metal (M = Mn, Re) for photoCORM: a DFT study. J Mol Model 29, 306 (2023). https://doi.org/10.1007/s00894-023-05712-3

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