Dataset Information

Density Functional Study of Metal-to-Ligand Charge Transfer and Hole-Hopping in Ruthenium(II) Complexes with Alkyl-Substituted Bipyridine Ligands.

ABSTRACT: In this study, we present a density functional study of four ruthenium complexes by means of UV-visible spectroscopy and Marcus theory. These molecules, [Ru^II(bipyP)(bipy)₂] (P1), [Ru^II(bipyP)(dmb)₂] (P2), [Ru^II(bipyP)(dtbb)₂] (P3), and [Ru^II(bipyP)(dnb)₂] (P4), where bipyP = 2,2'-bipyridine-4,4'-diphosphonic acid, bipy = 2,2'-bipyridine, dmb = 4,4'-dimethyl-2,2'-bipyridine, dtbb = 4,4'-di-tert-butyl-2,2'-bipyridine, and dnb = 4,4'-dinonyl-2,2'-bipyridine, are photosensitizers for applications in dye-sensitized photo-electrochemical cells (DSPECs). Because of the undetermined P4 conformation in the experiment, we modeled three P4 conformers with straight (P4-straight) and bent nonyl chains (P4-bend1 and bend2). UV-vis absorption spectra by time-dependent density functional theory showed intense metal-to-ligand charge transfer to anchor bipyridine ligands (MLCT-anchoring) at 445-460 nm, which accurately reproduce experimental data. The largest light-harvesting efficiency of the MLCT-anchoring state was observed in the P4-bend1 conformer, which has the lowest P4 energy. This may relate to greater electron injection in the P4 and supports experimental results of dye-only systems (do-DSPEC). The calculated charge transfer rates agree well with the experimental trend. The largest rate was obtained for P2, which was attributed to the expansion of the highest-occupied molecular orbital toward the ancillary bipy ligands and also to the short distances between dyes on the TiO₂ surface. These results also support experimental results for P2, which was the best compound for lateral hole-hopping in a sacrificial agent-containing system (sa-DSPEC).

SUBMITTER: Salmahaminati

PROVIDER: S-EPMC7807472 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Density Functional Study of Metal-to-Ligand Charge Transfer and Hole-Hopping in Ruthenium(II) Complexes with Alkyl-Substituted Bipyridine Ligands.

Salmahaminati Abe Minori M Purnama Indra I Mulyana Jacob Yan JY Hada Masahiko M

ACS omega 20201228 1

In this study, we present a density functional study of four ruthenium complexes by means of UV-visible spectroscopy and Marcus theory. These molecules, [RuII(bipyP)(bipy)2] (P1), [RuII(bipyP)(dmb)2] (P2), [RuII(bipyP)(dtbb)2] (P3), and [RuII(bipyP)(dnb)2] (P4), where bipyP = 2,2'-bipyridine-4,4'-diphosphonic acid, bipy = 2,2'-bipyridine, dmb = 4,4'-dimethyl-2,2'-bipyridine, dtbb = 4,4'-di-tert-butyl-2 ...[more]

PMID: 33458459

Similar Datasets

Project description:Cisplatin-based chemotherapy is a common regimen for bladder cancer, a life-threatening cancer with more than 500,000 new cases worldwide annually. Like many other metallodrugs, cisplatin causes severe side effects for its general toxicity. Organoruthenium is known for its structural stability, good anticancer activity, and possible low general toxicity. Here, we have prepared and characterized a series of water-soluble ruthenium-arene complexes with N,N'-chelating ligands: [Ru(II)-η6-arene-(4,4'-(X)2-2,2'-bipyridine)Cl]Cl (arene = p-cymene, X = C4H9 (1), COOH (2), COOCH3 (3), COOC2H5 (4); arene = benzene, X = C4H9 (5), COOCH3 (6), COOC2H5 (7)). These complexes are carefully characterized using single-crystal X-ray diffraction, UV-vis, IR, 1H NMR, and MALDI-TOF MS spectroscopy. Their DFT-calculated structural and thermodynamic properties are consistent with the experimental observations. Biophysicochemical studies of complex interaction with CTDNA and BSA supported by molecular docking simulations reveal suitable properties of 1-7 as anticancer agents. Cytotoxicities of 1-7 are evaluated on healthy human MCF-10a-breast epithelial and African green monkey Vero cells, and carcinoma human HepG-2-hepatic, T24-bladder, and EAhy-926-endothelial cells. All complexes exhibit much higher cytotoxicity for T24 than cisplatin. Particularly, 1 and 2 are also highly selective toward T24. Fluorescence imaging and flow cytometry demonstrate that 1 and 2 penetrate T24 cell membrane and induce early apoptosis at their respective IC50 concentrations, which ultimately lead to cell death. Statistical analysis suggests that the order of importance for T24 cell antiproliferation is protein binding, Log p, Ru-Cl bond length, while DNA binding is the least important. This study is the first to report the anti-bladder cancer efficacy of Ru-arene-2,2'-bipyridine complexes, and may provide insights for rational design of organoruthenium drugs in the enduring search for new chemotherapeutic agents.

Dataset Information

Density Functional Study of Metal-to-Ligand Charge Transfer and Hole-Hopping in Ruthenium(II) Complexes with Alkyl-Substituted Bipyridine Ligands.

Publications

Density Functional Study of Metal-to-Ligand Charge Transfer and Hole-Hopping in Ruthenium(II) Complexes with Alkyl-Substituted Bipyridine Ligands.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets