Ion valence-gated photochromism of an aza-crowned diarylethene.

A non-photochromic diarylethene 2o with an N-phenylaza-15-crown-5 was synthesized. When the nitrogen atom in the aza-crown ring was protonated, it became photochromic due to the prevention of a twisted intramolecular charge transfer (TICT). Although addition of a monovalent metal cation (Li, Na, K, Rb, Cs, Cu, Ag) in acetonitrile could not stop the TICT so that it was not photochromic, the addition of a multivalent metal cation (Mg, Ca, Sr, Ba, Fe, Ni, Al, Sb) changed 2o to be photochromic due to the strong attraction of the lone pair on the nitrogen atom.

On-Demand Chirality Transfer of Human Serum Albumin to Bis(thiophen-2-yl)hexafluorocyclopentenes through Their Photochromic Ring Closure.

Photochromic 1,2-bis(5-carboxy-3-methyl-2-thienyl)hexafluorocyclopentene and its dimethyl ester incorporated in human serum albumin (HSA) showed highly enantioselective photochromic ring-closing reactions upon 366 nm light irradiation. The absolute stereochemistry of the major ring-closed form of the dicarboxylic acid at the newly formed sp carbon atoms was determined to be () by the process of docking simulation of the diarylethene molecule and HSA followed by molecular dynamics calculations and comparison of the measured and calculated CD spectra. Esterification of the major closed form of the diacid gave the minor closed form of the diester.