Factors Controlling Cage Escape Yields of Closed- and Open-Shell Metal Complexes in Bimolecular Photoinduced Electron Transfer.

The cage escape yield, i.e., the separation of the geminate radical pair formed immediately after bimolecular excited-state electron transfer, was studied in 11 solvents using six Fe(III), Ru(II), and Ir(III) photosensitizers and tri--tolylamine as the electron donor.

Factors that Impact Photochemical Cage Escape Yields.

The utilization of visible light to mediate chemical reactions in fluid solutions has applications that range from solar fuel production to medicine and organic synthesis. These reactions are typically initiated by electron transfer between a photoexcited dye molecule (a photosensitizer) and a redox-active quencher to yield radical pairs that are intimately associated within a solvent cage. Many of these radicals undergo rapid thermodynamically favored "geminate" recombination and do not diffuse out of the solvent cage that surrounds them.

Investigation of the Excited-State Electron Transfer and Cage Escape Yields Between Halides and a Fe(III) Photosensitizer.

Excited-state quenching and reduction of [Fe(phtmeimb)], where phtmeimb is phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate, with iodide, bromide, and chloride were studied in dichloromethane, acetonitrile, and acetonitrile/water 1:1 mixture by means of steady-state and time-resolved spectroscopic techniques. Quenching rate constants were almost diffusion-limited in dichloromethane and acetonitrile and followed the expected periodic trend, i.e.

Photocatalytic conversion of aryl diazonium salts to sulfonyl fluorides.

Sulfonyl fluorides have emerged as powerful tools in chemical biology for the selective labelling of proteins. A photocatalytic method is described for the conversion of aryl diazonium salts to aryl sulfonyl fluorides. The diazonium substrates are easily obtained in one step from functionalized anilines.

A protocol for determining cage-escape yields using nanosecond transient absorption spectroscopy.

Here, we present a protocol for the determination of cage-escape yields following excited-state electron transfer between a photosensitizer and a quencher. We describe steps for determining changes in molar absorption coefficient of the different oxidation states via photolysis experiments and the percentage of reacted species via steady-state or time-resolved spectroscopy. We then detail measurement of the amount of formed product via nanosecond transient absorption spectroscopy.

Photosensitized Activation of Diazonium Derivatives for C-B Bond Formation.

Aryl diazonium salts are ubiquitous building blocks in chemistry, as they are useful radical precursors in organic synthesis as well as for the functionalization of solid materials. They can be reduced electrochemically or through a photo-induced electron transfer reaction. Here we provide a detailed picture of the ground and excited-state reactivity of a series of 9 rare and earth abundant photosensitizers with 13 aryl diazonium salts, which also included 3 macrocyclic calix[4]arene tetradiazonium salts.