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New ruthenium polypyridyl complexes as potential sensors of acetonitrile and catalysts for water oxidation.

ABSTRACT: New ruthenium(ii) polypyridyl complexes of formulae [RuCl(Me₂Ntrpy)(bpy-OMe)]Cl, 1, and [Ru(Me₂Ntrpy)(bpy-OMe)(OH₂)](CF₃SO₃)₂, 2, with Me₂Ntrpy = 4'-N,N-dimethylamino-2,2':6',2''-terpyridine and bpy-OMe = 4,4'-dimethoxy-2,2'-bipyridine, were synthetized and characterized by spectroscopic and electrochemical techniques. Besides, [Ru(Me₂Ntrpy)(bpy-OMe)(NCCH₃)]²⁺, 3, was obtained and characterized by UV-vis spectroscopy in acetonitrile solution. All experimental results were complemented with DFT and TD-DFT calculations. The complete structure of complex 1 was determined by X-ray diffraction, evidencing that the Ru-N and Ru-Cl bond lengths are longer than those determined in [RuCl(trpy)(bpy)](PF₆). The strong electron donating properties of the substituents of both bpy and trpy rings in complexes 1 and 2 led to their potential applications for detecting traces of acetonitrile as a contaminant in aqueous solutions of radiopharmaceuticals and to utilization of complex 2 as a promising candidate for catalyzing water oxidation processes.

SUBMITTER: Abate PO

PROVIDER: S-EPMC8984912 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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New ruthenium polypyridyl complexes as potential sensors of acetonitrile and catalysts for water oxidation.

Abate Pedro O PO Peyrot Analía M AM Fontrodona Xavier X Romero Isabel I Fagalde Florencia F Katz Néstor E NE

RSC advances 20220317 14

New ruthenium(ii) polypyridyl complexes of formulae [RuCl(Me2Ntrpy)(bpy-OMe)]Cl, 1, and [Ru(Me2Ntrpy)(bpy-OMe)(OH2)](CF3SO3)2, 2, with Me2Ntrpy = 4'-N,N-dimethylamino-2,2':6',2''-terpyridine and bpy-OMe = 4,4'-dimethoxy-2,2'-bipyridine, were synthetized and characterized by spectroscopic and electrochemical techniques. Besides, [Ru(Me2Ntrpy)(bpy-OMe)(NCCH3)]2+, 3, was obtai ...[more]

PMID: 35424825

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Project description:Metal complexes that release ligands upon photoexcitation are important tools for biological research and show great potential as highly specific therapeutics. Upon excitation with visible light, [Ru(TQA)(MeCN)2](2+) [TQA = tris(2-quinolinylmethyl)amine] exchanges one of the two acetonitriles (MeCNs), whereas [Ru(DPAbpy)MeCN](2+) [DPAbpy = N-(2,2'-bipyridin-6-yl)-N,N-bis(pyridin-2-ylmethyl)amine] does not release MeCN. Furthermore, [Ru(TQA)(MeCN)2](2+) is highly selective for release of the MeCN that is perpendicular to the plane of the two axial quinolines. Density functional theory calculations provide a clear explanation for the photodissociation behavior of these two complexes. Excitation by visible light and intersystem crossing leads to a six-coordinate (3)MLCT state. Dissociation of acetonitrile can occur after internal conversion to a dissociative (3)MC state, which has an occupied dσ* orbital that interacts in an antibonding fashion with acetonitrile. For [Ru(TQA)(MeCN)2](2+), the dissociative (3)MC state is lower than the (3)MLCT state. In contrast, the (3)MC state of [Ru(DPAbpy)MeCN](2+) that releases acetonitrile has an energy higher than that of the (3)MLCT state, indicating dissociation is unfavorable. These results are consistent with the experimental observations that efficient photodissociation of acetonitrile occurs for [Ru(TQA)(MeCN)2](2+) but not for [Ru(DPAbpy)MeCN](2+). For the release of the MeCN ligand in [Ru(TQA)(MeCN)2](2+) that is perpendicular to the axial quinoline rings, the (3)MLCT state has an occupied quinoline π* orbital that can interact with a dσ* Ru-NCCH3 antibonding orbital as the Ru-NCCH3 bond is stretched and the quinolines bend toward the departing acetonitrile. This reduces the barrier for the formation of the dissociative (3)MC state, leading to the selective photodissociation of this acetonitrile. By contrast, when the acetonitrile is in the plane of the quinolines or bpy, no interaction occurs between the ligand π* orbital and the dσ* Ru-NCCH3 orbital, resulting in high barriers for conversion to the corresponding (3)MC structures and no release of acetonitrile.

Dataset Information

New ruthenium polypyridyl complexes as potential sensors of acetonitrile and catalysts for water oxidation.

Publications

New ruthenium polypyridyl complexes as potential sensors of acetonitrile and catalysts for water oxidation.

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