Revealing the initial steps in homogeneous photocatalysis by time-resolved spectroscopy.

Photocatalysis attracts currently intense research since it can provide efficient routes for generating solar fuels and allows to apply sunlight for an environmentally friendly synthesis of valuable chemical compounds. Accordingly, in future photocatalysis may contribute significantly to a sustainable economy. However, up to now photocatalysis has made it only into some niche applications.

A domino reaction of 3-chlorochromones with aminoheterocycles. Synthesis of pyrazolopyridines and benzofuropyridines and their optical and ecto-5'-nucleotidase inhibitory effects.

A new and efficient domino reaction of 3-chlorochromones with electron-rich aminoheterocycles was developed which allows for a convenient synthesis of a variety of pyrazolo[3,4-b]pyridines, pyrrolo[2,3-b]pyridines, pyrido[2,3-d]pyrimidines and benzofuro[3,2-b]pyridines. The products exhibit strong fluorescence. In addition, they exhibit significant ecto-5'-nucleotidase inhibition properties and cytotoxic behavior.

The Connection between NHC Ligand Count and Photophysical Properties in Fe(II) Photosensitizers: An Experimental Study.

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.

Boosting Visible-Light-Driven Photocatalytic Hydrogen Evolution with an Integrated Nickel Phosphide-Carbon Nitride System.

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.

Novel synthesis of 5-methyl-5,10-dihydroindolo[3,2-b]indoles by Pd-catalyzed C-C and two-fold C-N coupling reactions.

A series of 5,10-dihydroindolo[3,2-b]indoles was successfully prepared by an efficient two-step strategy based on site-selective Pd-catalyzed cross-coupling reaction with N-methyl-2,3-dibromoindole and subsequent cyclization by two-fold Pd-catalyzed C-N coupling with amines. The products show a strong fluorescence.

Palladium catalyzed synthesis and physical properties of indolo[2,3-b]quinoxalines.

A series of indolo[2,3-b]quinoxaline derivatives were efficiently synthesized from 2,3-dibromoquinoxaline by two pathways. A one-pot approach using Pd-catalyzed two-fold C-N coupling and C-H activation reactions gave indolo[2,3-b]quinoxaline derivatives in good yields, but with limited substrate scope. In addition, a two-step approach to indolo[2,3-b]quinoxalines was developed which is based on Pd-catalyzed Suzuki coupling reactions and subsequent annulation by Pd-catalyzed two-fold C-N coupling with aromatic and aliphatic amines.

Electron- and Energy-Transfer Processes in a Photocatalytic System Based on an Ir(III)-Photosensitizer and an Iron Catalyst.

The reaction pathways of bis-(2-phenylpyridinato-)(2,2'-bipyridine)iridium(III)hexafluorophosphate [Ir(ppy)2(bpy)]PF6 within a photocatalytic water reduction system for hydrogen generation based on an iron-catalyst were investigated by employing time-resolved photoluminescence spectroscopy and time-dependent density functional theory. Electron transfer (ET) from the sacrificial reagent to the photoexcited Ir complex has a surprisingly low probability of 0.4% per collision.

A noble-metal-free system for photocatalytic hydrogen production from water.

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.

Photocatalytic water reduction with copper-based photosensitizers: a noble-metal-free system.

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.