Photodeoxygenation of dinaphthothiophene, benzophenanthrothiophene, and benzonaphthothiophene S-oxides.

Photoinduced deoxygenation of dibenzothiophene S-oxide (DBTO) has been suggested to release atomic oxygen [O((3)P)]. To expand the conditions and applications where O((3)P) could be used, generation of O((3)P) at longer wavelengths was desirable. The sulfoxides benzo[b]naphtho-[1,2,d]thiophene S-oxide, benzo[b]naphtho[2,1,d]thiophene S-oxide, benzo[b]phenanthro[9,10-d]thiophene S-oxide, dinaphtho[2,1-b:1',2'-d]thiophene S-oxide, and dinaphtho[1,2-b:2',1'-d]thiophene S-oxide all absorb light at longer wavelengths than DBTO. To determine if these sulfoxides could be used to generate O((3)P), quantum yield studies, product studies, and computational analysis were performed. Quantum yields for the deoxygenation were up to 3 times larger for these sulfoxides compared to DBTO. However, oxidation of the solvent by these sulfoxides resulted in different ratios of oxidized products compared to DBTO, which suggested a change in deoxygenation mechanism. Density functional calculations revealed a much larger singlet-triplet gap for the larger sulfoxides compared to DBTO. This led to the conclusion that the examined sulfoxides could undergo deoxygenation by two different mechanisms.

Propagation dynamics of optical vortices due to Gouy phase.

We study the propagation of off-axis vortices in a paraxial beam formed by two collinear Laguerre-Gauss beams. We show that the vortices move about the beam axis as the light propagates resulting in a rotation of the beam's transverse profile. This rotation is explained by the Gouy phase acquired by the component beams. Experimental measurements of the angular position of the vortices are in good agreement with a two-mode theory.