Rhenium(I) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction

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Abstract

Summary

A photochemical reduction of CO₂ to CO or formic acid was shown using the bipyridine-based rhenium, ruthenium and manganese catalysts [Re(bpy)(CO)3(MeCN)][PF6] (100781), Ru(dtBubpy)(CO)2Cl2 (100573) or Molecule with key WCQGNVNGTWFVLO-UHFFFAOYSA-N does not exist. in combination with cyclic rhenium-based trinuclear redox photosensitizers. Turnover numbers (TONs) of up to 290 for formic acid were reached in DMA with the ruthenium complex Ru(dtBubpy)(CO)2Cl2 (100573) and photosensitizer Molecule with key KSOIVZAANOLODS-UHFFFAOYSA-T does not exist.. For CO production, TONs of up to 98 were obtained in DMF with the rhenium complex [Re(bpy)(CO)3(MeCN)][PF6] (100781) and photosensitizer Molecule with key LOLRMPNEYKEGPF-UHFFFAOYSA-T does not exist.. The experiments were conducted under visible-light irradiation (λ = 436 nm) using TEOA as sacrificial electron donor (see section SEDs below).

Advances and special progress

Re(I)-based trinuclear photosensitizers were developed and allowed for high product selectivities for CO or formic acid in CO₂ reduction attempts with different bipyridine-based catalysts.

Content of the published article in detail

The article contains results for the reduction of CO₂ to CO or formic acid under visible-light catalysis using bipyridine-based complexes and rhenium-based trinuclear rings as photosensitizers. The catalytic system performs best (referring to the TON of formate production) in DMA and in DMF for CO production.

Catalyst

[Re(bpy)(CO)3(MeCN)][PF6] (100781) Ru(dtBubpy)(CO)2Cl2 (100573)

Photosensitizer

Investigation

		cat	cat conc [µM]	PS	PS conc [mM]	solvent A	.	.	λexc [nm]	.	TON CO	.	.	.	.
(edit)	1.	[Re(bpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100878	0.05	DMF			436		27
(edit)	2.	[Re(bpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100878	0.05	DMF			436		98
(edit)	3.	[Re(bpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100877	0.05	DMF			436		22
(edit)	4.	[Re(bpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100877	0.05	DMF			436		71
(edit)	5.			Molecule:100877	0.05	DMF			436		6
(edit)	6.			Molecule:100877	0.05	DMF			436		8
(edit)	7.	[Re(bpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100879	0.05	DMF			436		20
(edit)	8.	[Re(bpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100879	0.05	DMF			436		32
(edit)	9.	[Re(bpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100880	0.05	DMF			436		11
(edit)	10.	[Re(bpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100880	0.05	DMF			436		48

Investigation-Name: Table 1

		cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	.	.	λexc [nm]	.	TON CO	TON H2	TON HCOOH	.	.	.	.
(edit)	1.	Ru(dtBubpy)(CO)2Cl2	0.05	Molecule:100877	0.05			DMF			436		20	72	290
(edit)	2.	Ru(dtBubpy)(CO)2Cl2	0.05	Molecule:100877	0.05	BI(OH)H	0.03	DMF			436		16	49	280
(edit)	3.	[Mn(dtBubpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100877	0.05			DMF			436		32		85
(edit)	4.	[Mn(dtBubpy)(CO)3(MeCN)][PF6]	0.05	Molecule:100877	0.05	BI(OH)H	0.03	DMF			436		80		60

Investigation-Name: Table 2

Sacrificial Electron Donor

In this study, the experiments were done with the sacrificial electron donor TEOA (100507).

Additives

In this study, no additives were tested.