Theoretical investigation of solvent and oxidation/deprotonation effects on the electronic structure of a mononuclear Ru-aqua-polypyridine complex in aqueous solution

Franco, Leandro Rezende; Toledo, Kalil Cristhian Figueiredo; Matias, Tiago Araujo; Araujo, C. Moyses; Araki, Koiti; Coutinho, Kaline

doi:10.1039/d3cp02154h

Phys. Chem. Chem. Phys.

2023

DOI: 10.1039/d3cp02154h

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Theoretical investigation of solvent and oxidation/deprotonation effects on the electronic structure of a mononuclear Ru-aqua-polypyridine complex in aqueous solution

Leandro Rezende Franco,

Kalil Cristhian Figueiredo Toledo,

Tiago Araujo Matias

et al.

Abstract: Ru-aqua complex in water, showcasing Ru atom, coordinated water, and hydrogen bonds on left; UV-Vis spectrum and comparison to experiment on right. QM/MM approach emphasized.

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Cited by 2 publications

References 113 publications

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Dipicolinate‐Ruthenium‐NHC/trpy Complexes: Pincer Ligand Induced Hemilability of Dipicolinate and Enhancement of Cytotoxic Property

Dhibar,

Chandra,

Kundu

et al. 2024

Eur J Inorg Chem

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A ruthenium(II) aquo complex [Ru(dipic)(PPh3)2(OH2)], (1A), bearing O,N,O‐coordinated 2,6‐dipicolinate was synthesized via reaction of [Ru(PPh3)3Cl2] with 2,6‐dipicolinic acid. Crystal structure of 1A was determined. Utilizing 1A as a synthon, three new complexes were synthesized. Reaction of 1A with 1‐methyl‐3‐(2ʹ‐pyridyl)imidazole (IMeCN), afforded [Ru(dipic)(IMeCN)(PPh3)], (2A). Similar reactions of 1A with two pincer ligands, viz. 2,6‐bis(1ʹ‐methyl imidazolyl)pyridine (IMeCNC) and 2,2';6',2"‐terpyridine (trpy), respectively yielded [Ru(dipic)(IMeCNC)(PPh3)], (3A) and [Ru(dipic)(trpy)(PPh3)], (3B). Structure of 2A was optimized by DFT. Structures of 3A and 3B were determined by X‐ray crystallography. In both 3A and 3B the 2,6‐dipicolinate ligand was found to be N,O‐coordinated with one carboxy end remaining unbound to the metal center. Anticancer property of 2A, 3A and 3B was studied and compared. Cytotoxicity of 3A, studied against chronic myelogenous leukemia cell line (K562), hepatocellular carcinoma cell line (HepG2) and breast adenocarcinoma cell line (MCF7) was found to be the most promising. It displayed the best activity against K562, while it did not have any appreciable effect on its normal counterpart, viz. hPBMC. The comparative cytotoxicity studies indicated that presence of the pincer NHC ligand in 3A, together with presence of the free carboxylate end of N,O‐coordinated dipic ligand, are presumably responsible for its superior cytotoxic behavior.

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Dipicolinate‐Ruthenium‐NHC/trpy Complexes: Pincer Ligand Induced Hemilability of Dipicolinate and Enhancement of Cytotoxic Property

Dhibar,

Chandra,

Kundu

et al. 2024

Eur J Inorg Chem

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Unveiling the impact of exchange-correlation functionals on the description of key electronic properties of non-fullerene acceptors in organic photovoltaics

Franco,

Marchiori,

Araujo

2023

The Journal of Chemical Physics

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Non-fullerene electron acceptors have emerged as promising alternatives to traditional electron-acceptors in the active layers of organic photovoltaics. This is due to their tunable energy levels, optical response in the visible light spectrum, high electron mobility, and photochemical stability. In this study, the electronic properties of two representative non-fullerene acceptors, ITIC and Y5, have been calculated within the framework of density functional theory using a range of hybrid and non-hybrid density functionals. Screened range-separated hybrid (SRSH) approaches were also tested. The results are analyzed in light of the previously reported experimental outcomes. Specifically, we have calculated the oxidation and reduction potentials, fundamental and optical gaps, the highest occupied molecular orbital and lowest unoccupied molecular orbital energies, and exciton binding energies. Additionally, we have investigated the effects of the medium dielectric constant on these properties employing a universal implicit solvent model. It was found that hybrid functionals generally perform poorly in predicting oxidation potentials, while non-hybrid functionals tend to overestimate reduction potentials. The inclusion of a large Hartree–Fock contribution to the global or long range was identified as the source of inaccuracy for many hybrid functionals in predicting both redox potentials and the fundamental and optical gaps. Corroborating with the available literature, ∼50% of all tested functionals predicted very small exciton binding energies, within the range of ±0.1 eV, that become even smaller by increasing the dielectric constant of the material. Finally, the OHSE2PBE and tHCTHhyb functionals and the optimal tuning SRSH approach emerged as the best-performing methods, with good accuracy in the description of the electronic properties of interest.

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Theoretical investigation of solvent and oxidation/deprotonation effects on the electronic structure of a mononuclear Ru-aqua-polypyridine complex in aqueous solution

Abstract: Ru-aqua complex in water, showcasing Ru atom, coordinated water, and hydrogen bonds on left; UV-Vis spectrum and comparison to experiment on right. QM/MM approach emphasized.

Cited by 2 publications

References 113 publications

Dipicolinate‐Ruthenium‐NHC/trpy Complexes: Pincer Ligand Induced Hemilability of Dipicolinate and Enhancement of Cytotoxic Property

Dipicolinate‐Ruthenium‐NHC/trpy Complexes: Pincer Ligand Induced Hemilability of Dipicolinate and Enhancement of Cytotoxic Property

Unveiling the impact of exchange-correlation functionals on the description of key electronic properties of non-fullerene acceptors in organic photovoltaics

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