Dataset Information

Not All ³MC States Are the Same: The Role of ³MC_cis States in the Photochemical N^∧N Ligand Release from [Ru(bpy)₂(N^∧N)]²⁺ Complexes.

ABSTRACT: Ruthenium(II) complexes feature prominently in the development of agents for photoactivated chemotherapy; however, the excited-state mechanisms by which photochemical ligand release operates remain unclear. We report here a systematic experimental and computational study of a series of complexes [Ru(bpy)₂(N^∧N)]²⁺ (bpy = 2,2'-bipyridyl; N^∧N = bpy (1), 6-methyl-2,2'-bipyridyl (2), 6,6'-dimethyl-2,2'-bipyridyl (3), 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole (4), 1-benzyl-4-(6-methylpyrid-2-yl)-1,2,3-triazole (5), 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl (6)), in which we probe the contribution to the promotion of photochemical N^∧N ligand release of the introduction of sterically encumbering methyl substituents and the electronic effect of replacement of pyridine by 1,2,3-triazole donors in the N^∧N ligand. Complexes 2 to 6 all release the ligand N^∧N on irradiation in acetonitrile solution to yield cis-[Ru(bpy)₂(NCMe)₂]²⁺, with resultant photorelease quantum yields that at first seem counter-intuitive and span a broad range. The data show that incorporation of a single sterically encumbering methyl substituent on the N^∧N ligand (2 and 5) leads to a significantly enhanced rate of triplet metal-to-ligand charge-transfer (³MLCT) state deactivation but with little promotion of photoreactivity, whereas replacement of pyridine by triazole donors (4 and 6) leads to a similar rate of ³MLCT deactivation but with much greater photochemical reactivity. The data reported here, discussed in conjunction with previously reported data on related complexes, suggest that monomethylation in 2 and 5 sterically inhibits the formation of a ³MC_cis state but promotes the population of ³MC_trans states which rapidly deactivate ³MLCT states and are prone to mediating ground-state recovery. On the other hand, increased photochemical reactivity in 4 and 6 seems to stem from the accessibility of ³MC_cis states. The data provide important insights into the excited-state mechanism of photochemical ligand release by Ru(II) tris-bidentate complexes.

SUBMITTER: Eastham K

PROVIDER: S-EPMC9749030 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

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Publications

Not All 3MC States Are the Same: The Role of 3MCcis States in the Photochemical N∧N Ligand Release from [Ru(bpy)2(N∧N)]2+ Complexes.

Eastham Katie K Scattergood Paul A PA Chu Danny D Boota Rayhaan Z RZ Soupart Adrien A Alary Fabienne F Dixon Isabelle M IM Rice Craig R CR Hardman Samantha J O SJO Elliott Paul I P PIP

Inorganic chemistry 20221130 49

Ruthenium(II) complexes feature prominently in the development of agents for photoactivated chemotherapy; however, the excited-state mechanisms by which photochemical ligand release operates remain unclear. We report here a systematic experimental and computational study of a series of complexes [Ru(bpy)2(N∧N)]2+ (bpy = 2,2'-bipyridyl; N∧N = bpy (1), 6-methyl-2,2'-bipyridyl (2), 6,6'-dimethyl-2,2'-bipyridyl (3), 1-benzyl-4-(pyrid-2 ...[more]

PMID: 36450138

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Project description:Photochemical CO2 reduction catalysed by trans(Cl)-Ru(bpy)(CO)2Cl2 (bpy = 2,2'-bipyridine) efficiently produces carbon monoxide (CO) and formate (HCOO-) in N,N-dimethylacetamide (DMA)/water containing [Ru(bpy)3]2+ as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor. We have unexpectedly found catalyst concentration dependence of the product ratio (CO/HCOO-) in the photochemical CO2 reduction: the ratio of CO/HCOO- decreases with increasing catalyst concentration. The result has led us to propose a new mechanism in which HCOO- is selectively produced by the formation of a Ru(i)-Ru(i) dimer as the catalyst intermediate. This reaction mechanism predicts that the Ru-Ru bond dissociates in the reaction of the dimer with CO2, and that the insufficient electron supply to the catalyst results in the dominant formation of HCOO-. The proposed mechanism is supported by the result that the time-course profiles of CO and HCOO- in the photochemical CO2 reduction catalysed by [Ru(bpy)(CO)2Cl]2 (0.05 mM) are very similar to those of the reduction catalysed by trans(Cl)-Ru(bpy)(CO)2Cl2 (0.10 mM), and that HCOO- formation becomes dominant under low-intensity light. The kinetic analyses based on the proposed mechanism could excellently reproduce the unusual catalyst concentration effect on the product ratio. The catalyst concentration effect observed in the photochemical CO2 reduction using [Ru(4dmbpy)3]2+ (4dmbpy = 4,4'-dimethyl-2,2'-bipyridine) instead of [Ru(bpy)3]2+ as the photosensitizer is also explained with the kinetic analyses, reflecting the smaller quenching rate constant of excited [Ru(4dmbpy)3]2+ by BNAH than that of excited [Ru(bpy)3]2+. We have further synthesized trans(Cl)-Ru(6Mes-bpy)(CO)2Cl2 (6Mes-bpy = 6,6'-dimesityl-2,2'-bipyridine), which bears bulky substituents at the 6,6'-positions in the 2,2'-bipyridyl ligand, so that the ruthenium complex cannot form the dimer due to the steric hindrance. We have found that this ruthenium complex selectively produces CO, which strongly supports the catalytic mechanism proposed in this work.

Dataset Information

Not All ³MC States Are the Same: The Role of ³MC_cis States in the Photochemical N^∧N Ligand Release from [Ru(bpy)₂(N^∧N)]²⁺ Complexes.

Publications

Not All <sup>3</sup>MC States Are the Same: The Role of <sup>3</sup>MC<sub>cis</sub> States in the Photochemical N<sup>∧</sup>N Ligand Release from [Ru(bpy)<sub>2</sub>(N<sup>∧</sup>N)]<sup>2+</sup> Complexes.

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