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The invention of efficient systems for the photocatalytic reduction of CO comprising earth-abundant metal catalysts is a promising approach for the production of solar fuels. One bottleneck is to design highly selective and robust molecular complexes that are able to transform the CO gas. The Cu quaterpyridine complex [Cu(qpy)] (1) is found to be a highly efficient and selective catalyst for visible-light driven CO reduction in CH CN using [Ru(bpy) ] (bpy: bipyridine) as photosensitizer and BIH/TEOA (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole/triethanolamine) as sacrificial reductant. The photocatalytic reaction is greatly enhanced by the presence of H O (1-4 % v/v), and a turnover number of >12 400 for CO production can be achieved with 97 % selectivity, which is among the highest of molecular 3d CO reduction catalysts. Results from Hg poisoning and dynamic light scattering experiments suggest that this photocatalyst is homogenous. To the best of our knowledge, 1 is the first example of molecular Cu-based catalyst for the photoreduction of CO .

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A series of nickel(II) complexes bearing tetradentate macrocyclic N 4 , N 3 S and N 3 P ligands were synthesized and their photocatalytic activity towards proton reduction has been investigated by using [Ir(dF(CF 3 )ppy) 2 (dmbpy)]PF 6 (dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5trifluoromethylpyridine and dmbpy = 4,4'-dimethyl-2,2'-dipyridyl) as the photosensitizer and

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This tutorial describes recent developments in the use of metal quaterpyridine complexes as electrocatalysts and photocatalysts for water splitting and CO2 reduction.

In recent years, various organic dyes have been used as photosensitizers for the photocatalytic reduction of water and carbon dioxide, which is a sustainable approach for fuel generation under noble-metal free conditions. Recent development of organic chromophores, which are characterized by a populated triplet excited state, have greatly facilitated their applications in solar fuel production. In this review, the photophysical properties of organic dyes are discussed in relation to their applications in photocatalytic reduction of water and carbon dioxide. In particular, common synthetic strategies for enhancing the population of their triplet states, which are important in promoting photoredox reactions, are described. This is followed by a review on recent developments of photocatalytic reduction of water and carbon dioxide involving various organic photosensitizers.

A series of homoleptic mononuclear 8-coordinate Fe and Co compounds, [Fe(L)](ClO) (2), [Fe(L)](ClO) (3), [Fe(L)](ClO) (4), [Co(L)](ClO) (5), [Co(L)](ClO) (6), [Co(L)](ClO) (7), and [Co(L)](ClO) (8) (L and L are 2,9-dialkylcarboxylate-1,10-phenanthroline ligands; L and L are 6,6'-dialkylcarboxylate-2,2'-bipyridine ligands), have been obtained, and their crystal structures have been determined by X-ray crystallography. The metal center in all of these compounds has an oversaturated coordination number of 8, which is completed by two neutral homoleptic tetradentate ligands and is unconventional in 3d-metal compounds. These compounds are further characterized by electronic spectroscopy, cyclic voltammetry (CV), and magnetic measurements. CV measurements of these complexes in MeCN solution exhibit rich redox properties. Magnetic measurements on these compounds demonstrate that the observed single-ion magnetic (SIM) behavior in the previously reported [Fe(L)](ClO) (1) is not a contingent case, since all of the 8-coordinate compounds 2-8 exhibit interesting slow magnetic relaxation under applied direct current fields.