A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids.

Aryl halides are a fundamental motif in synthetic chemistry, playing a critical role in metal-mediated cross-coupling reactions and serving as important scaffolds in drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope of existing halodecarboxylation methods remains limited, and there currently exists no unified strategy that provides access to any type of aryl halide from an aryl carboxylic acid precursor. Herein, we report a general catalytic method for direct decarboxylative halogenation of (hetero)aryl carboxylic acids via ligand-to-metal charge transfer. This strategy accommodates an exceptionally broad scope of substrates. We leverage an aryl radical intermediate toward divergent functionalization pathways: (1) atom transfer to access bromo- or iodo(hetero)arenes or (2) radical capture by copper and subsequent reductive elimination to generate chloro- or fluoro(hetero)arenes. The proposed ligand-to-metal charge transfer mechanism is supported through an array of spectroscopic studies.

Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear PtII →GeIV Complex.

Searching for a connection between the two-electron redox behavior of Group-14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o-(Ph2 P)C6 H4 )2 GeIV Cl2 ]PtII Cl2 and [(o-(Ph2 P)C6 H4 )2 ClGeIII ]PtIII Cl3 , two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o-(Ph2 P)C6 H4 )2 ClGeIII ]PtI Cl with quantum yields of 1.7 % and 3.2 % for the GeIV -PtII and GeIII -PtIII isomers, respectively. Conversion of the GeIV -PtII isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Finally, transient-absorption-spectroscopy studies carried out on the GeIII -PtIII isomer point to a ligand arene-Cl. charge-transfer complex as an intermediate.

The Role of Order in the Amplification of Light-Energy Conversion in a Dye-Sensitized Solar Cell Coupled to a Photonic Crystal.

We investigate the cause of amplification of light-energy conversion when coupling a nc-TiO2 film to a TiO2 inverse opal by comparing it to an inverse TiO2 glass (i-TiO2 -g) fabricated with the exact monodisperse air-hole size as an inverse opal with a stop band at 600 nm (600-i-TiO2 -o). A significant twofold average gain in the photon-to-current conversion efficiency is measured to the red of the stop band at the 600-i-TiO2 -o/nc-TiO2 bilayer under front-wall and back-wall illumination, greater than the gain within the stop band. A smaller amplification is measured under front-wall illumination-and no gain is measured under back-wall illumination-for i-TiO2 -g/nc-TiO2 at these energies. The photonic crystal therefore causes trapping of light through the bilayer, not only within the gap but also to the red, at frequencies within its dielectric band. This light-trapping effect is found to be dependent on structural order, as a highly disordered inverse glass film with the same air-hole size and thickness does not yield the same gain. A drop in the transmission of light is measured within the same frequencies to the red of the stop band upon adding nc-TiO2 to 600-i-TiO2 -o, consistent with light trapping in the bilayer.

Copper(II)-photocatalyzed decarboxylative oxygenation of carboxylic acids.

Showcasing the concept of light-induced homolysis for the generation of radicals, the CuII-photocatalyzed decarboxylative oxygenation of carboxylic acids with molecular oxygen as the terminal oxidant is described. Two CuII-carboxylate complexes with different coordination geometries were synthesized and characterized by X-ray analysis, correlating their structure with their ability to initiate light-induced decarboxylations.

Direct Evidence of Visible Light-Induced Homolysis in Chlorobis(2,9-dimethyl-1,10-phenanthroline)copper(II).

Developments in the field of photoredox catalysis that leveraged the long-lived excited states of Ir(III) and Ru(II) photosensitizers to enable radical coupling processes paved the way for explorations of synthetic transformations that would otherwise remain unrealized. While first row transition metal photocatalysts have not been as extensively investigated, valuable synthetic transformations covering broad scopes of olefin functionalization have been recently reported featuring photoactivated chlorobis(phenanthroline) Cu(II) complexes. In this study, the photochemical processes underpinning the catalytic activity of [Cu(dmp)2Cl]Cl (dmp = 2,9-dimethyl-1,10-phenanthroline) were studied. The combined results from static spectroscopic measurements and conventional photochemistry, ultrafast transient absorption, and electron paramagnetic resonance spin trapping experiments strongly support blue light (λex = 427 or 470 nm)-induced Cu-Cl homolytic bond cleavage in [Cu(dmp)2Cl]+ occurring in <100 fs. On the basis of electronic structure calculations, this bond-breaking photochemistry corresponds to the Cl → Cu(II) ligand-to-metal charge transfer transition, unmasking a Cu(I) species [Cu(dmp)2]+ and a Cl atom, thereby serving as a departure point for both Cu(I)- or Cu(II)-based photoredox transformations. No net photochemistry was observed through direct excitation of the ligand-field transitions in the red (λex = 785 or 800 nm), and all combined experiments indicated no evidence of Cu-Cl bond cleavage under these conditions. The underlying visible light-induced homolysis of a metal-ligand bond yielding a one-electron-reduced photosensitizer and a radical species may form the basis for novel transformations initiated by photoinduced homolysis featuring in situ-formed metal-substrate adducts utilizing first row transition metal complexes.

High photo-currents with a zwitterionic thiocyanate-free dye in aqueous-based dye sensitized solar cells.

We report a new water soluble and stable thiolate/disulfide redox couple (T(-)/DS) and its use with a new zwitterionic and thiocyanate-free dye (T169) in a 100% aqueous electrolyte system. A DSSC incorporating T169 and the T(-)/DS showed the highest photocurrents (Jsc = 13.30 mA cm(-2)) and IPCE% (84%) values reported to date. In addition, a 2000 h long-term stability measurement was performed, where Jsc and Voc of the above mentioned DSSC stayed somehow the same except for the fill factor (FF) which decreased from 0.62 to 0.48 and consequently lowered the total efficiency (from η = 4.5% on day 1 to η = 3.3% after 2000 h).