A series of heteroleptic copper(I) complexes with bidentate PP and NN chelate ligands was prepared and successfully applied as photosensitizers in the light-driven production of hydrogen, by using [Fe3(CO)12] as a water-reduction catalyst (WRC). These systems efficiently reduces protons from water/THF/triethylamine mixtures, in which the amine serves as a sacrificial electron donor (SR). Turnover numbers (for H) up to 1330 were obtained with these fully noble-metal-free systems. The new complexes were electrochemically and photophysically characterized. They exhibited a correlation between the lifetimes of the MLCT excited state and their efficiency as photosensitizers in proton-reduction systems. Within these experiments, considerably long excited-state lifetimes of up to 54 μs were observed. Quenching studies with the SR, in the presence and absence of the WRC, showed that intramolecular deactivation was more efficient in the former case, thus suggesting the predominance of an oxidative quenching pathway.

Of noble descent: a fully noble-metal-free system for the photocatalytic reduction of water at room temperature has been developed. This system consists of Cu(I) complexes as photosensitizers and [Fe(3)(CO)(12)] as the water-reduction catalyst. The novel Cu-based photosensitizers are relatively inexpensive, readily available from commercial sources, and stable to ambient conditions, thus making them an attractive alternative to the widely used noble-metal based systems.

Four homo- and heteroleptic complexes bearing both polypyridyl units and N-heterocyclic carbene (NHC) donor functions are studied as potential noble metal-free photosensitizers. The complexes [Fe(L1)(terpy)][PF], [Fe(L2)][PF], [Fe(L1)(L3)][PF], and [Fe(L3)][PF] (terpy = 2,2':6',2″ terpyridine, L1 = 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine, L2 = 2,6-bis[3-isopropylimidazol-2-ylidene]pyridine, L3 = 1-(2,2'-bipyridyl)-3-methylimidazol-2-ylidene) contain tridentate ligands of the C^N^C and N^N^C type, respectively, resulting in a Fe-NHC number between two and four. Thorough ground state characterization by single crystal diffraction, electrochemistry, valence-to-core X-ray emission spectroscopy (VtC-XES), and high energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) in combination with ab initio calculations show a correlation between the geometric and electronic structure of these new compounds and the number of the NHC donor functions. These results serve as a basis for the investigation of the excited states by ultrafast transient absorption spectroscopy, where the lifetime of the MLCT states is found to increase with the NHC donor count. The results demonstrate for the first time the close interplay between the number of NHC functionalities in Fe(II) complexes and their photochemical properties, as revealed in a comparison of the activity as photosensitizers in photocatalytic proton reduction.

The chromium(III) sensitizer [Cr(ddpd)2]3+ (ddpd=N,N′‐dimethyl‐N,N′‐dipyridine‐2‐ylpyridine‐2,6‐diamine), based on an earth‐abundant metal centre, possesses a unique excited‐state potential‐energy landscape. The very large energy gap between the redox‐active and substitutionally labile 4T2 state and the long‐lived low‐energy 2E spin‐flip state enables a selective, efficient sensitization of triplet dioxygen to give singlet dioxygen. Ultrafast intersystem crossing after the Franck Condon point from the 4T2 to the 2E excited state within 3.5 ps precludes intermolecular electron‐transfer pathways from the ultrashort‐lived excited 4T2 state. This specific excited‐state reactivity enables a selective visible‐light‐induced C−H bond activation of tertiary amines with 1O2 and subsequent trapping with cyanide to yield α‐aminonitriles in good to excellent yields.

Solar light harvesting by photocatalytic H evolution from water could solve the problem of greenhouse gas emission from fossil fuels with alternative clean energy. However, the development of more efficient and robust catalytic systems remains a great challenge for the technological use on a large scale. Here we report the synthesis of a sol-gel prepared mesoporous graphitic carbon nitride (sg-CN) combined with nickel phosphide (Ni P) which acts as a superior co-catalyst for efficient photocatalytic H evolution by visible light. This integrated system shows a much higher catalytic activity than the physical mixture of Ni P and sg-CN or metallic nickel on sg-CN under similar conditions. Time-resolved photoluminescence and electron paramagnetic resonance (EPR) spectroscopic studies revealed that the enhanced carrier transfer at the Ni P-sg-CN heterojunction is the prime source for improved activity.