Synthetic chemistry via radicals generated by photoinduced electron transfer

Synthetic control over photoinduced electron transfer in phosphorescence zinc sensors.

Despite the promising photofunctionalities, phosphorescent probes have been examined only to a limited extent, and the molecular features that provide convenient handles for controlling the phosphorescence response have yet to be identified. We synthesized a series of phosphorescence zinc sensors based on a cyclometalated heteroleptic Ir(III) complex. The sensor construct includes two anionic c...

Nonequilibrium photoinduced electron transfer

Cycloreversion of β-lactams via photoinduced electron transfer.

The radical anions of β-lactams, photogenerated in the presence of DABCO as an electron donor, undergo cycloreversion via N-C4 bond cleavage, back electron transfer and final C2-C3 bond cleavage, leading to olefins. The involved intermediates are 1,4-radical anions and 1,4-biradicals. The experimental observations are consistent with the results of DFT calculations.

Regio- and stereoselective functionalization of electron-deficient alkenes by organosilicon compounds via photoinduced electron transfer*

Regioand stereoselective photoallylation of electron-deficient alkenes by use of allylic silanes via photoinduced electron transfer has been described. Similar photoinduced functionalization reactions such as arylmethylation, alkylation, and silylation can be achieved by using a variety of organosilicon compounds. These photoreactions proceed via radical cations of organosilicon compounds and r...

Probing conformational dynamics in single donor-acceptor synthetic molecules by means of photoinduced reversible electron transfer.

We use single-molecule fluorescence lifetimes to probe dynamics of photoinduced reversible electron transfer occurring between triphenylamine (donor) and perylenediimide (acceptor) in single molecules of a polyphenylenic rigid dendrimer embedded in polystyrene. Here, reversible electron transfer in individual donor-acceptor molecules results in delayed fluorescence that is emitted with a high p...