Illuminating Photoswitchable Catalysis

Through the realization of conceptually new approaches aimed at controlling chemical reactions using light, the field of photoswitchable catalysis has seen rapid development over the past three decades. Although many photoswitchable catalysts are heterogeneous and utilize photosensitive surfaces, such as TiO2 and CdSe, significant attention has also been directed toward homogeneous analogues, primarily by capitalizing on the steric changes that accompany the E -> Z photoisomerizations of azobenzene or stilbene derivatives. More recently, photochromic diarylethene moieties have been used to switch the intrinsic catalytic activities and selectivities through alteration of the steric and electronic properties displayed by a supporting ligand. In addition to detailing the aforementioned advances, this perspective summarizes other important developments in photoswitchable catalysis and offers a viewpoint on the future outlook of the field

Switchable Mesomeric Betaines Derived from Pyridinium‐Phenolates and Bis(thienyl)ethane

Syntheses of push–pull substituted non-symmetric bis(thienyl)ethenes (BTEs) possessing a central perfluorocyclopentene core are described. The substituent effects of anisole, phenole, and phenolate as well as pyridine, pyridinium, and N-methylpyridinium substituents, joined through their 3- or 4-positions to the central BTE core, respectively, cover the range from very strongly electron-donating [σ(4-phenolate)=−1.00] to extremely strongly electron-withdrawing [σ(pyridinium-4-yl)=+2.57] in the title mesomeric betaines. The different isomers possessing 4-yl/4-yl, 4-yl/3-yl and 3-yl/3-yl substituents represent different combinations of conjugated and cross-conjugated partial structures and cause different spectroscopic properties. In addition, through-space conjugation between the 2- and 2′-position of the thiophenes can be observed which circumvents the charge-separation of through-bond cross-conjugation. The BTE possessing the push–pull chromophore consisting of 3-anisole and 4-pyridinium substituents (24) displays the best extinction coefficients within the series of compounds described here (ϵ=33.8/15.7 L/mol ⋅ cm), while the mesomeric betaine possessing an N-methylpyridinium-4-yl and a 4-phenolate substituent (29) displays considerable bathochromic shifts to λmax=724 nm in its closed form