Substituted Dibenzodiazocines: Rapid Synthesis and Photochemical Properties

Abstract

11,12-Dihydrodibenzo­[c,g]-1,2-diazocines have been established as a viable alternative to azobenzene for photoswitching, in particular, as they show an inverted switching behavior: the ground state is the Z isomer. In this paper, we present an improved method to obtain dibenzodiazocine and its derivatives from the respective 2-nitrotoluenes in two reaction steps, each proceeding in minutes. This fast access to a variety of derivatives permitted the study of substitution effects on the synthesis and on the photochemical properties. With biochemical applications in mind, methanol was chosen as a protic solvent system for the photochemical investigations. In contrast to the azobenzene system, none of the tested substitution patterns resulted in more efficient switching or in significantly prolonged half-lives, showing that the system is dominated by the ring strain.

Visible‐light‐switchable azobenzenes: Molecular design, supramolecular systems, and applications

“…In 2021, Klockmann et al. reported the rapid synthesis and tuning of the photochemical properties of dibenzodiazocines via the substitution of different ring positions with different substituents 56 . Effects of substituents on photochemical properties of diazocine are less pronounced than that of unsubstituted AB.…”

Inducing Motions of Polymers in Liquid Nitrogen with Light

“…General: Synthesis of monomers (BAzoDMA, AzoDMA, AzoDA, BCMA, BCA, and Bz6A) and photoisomerization behavior of BAzoDMA were described in Supporting Information. [46][47][48][49][50][51] NMR spectra were recorded on JEOL JNM-ECZ500R or Varian Mercury 400 spectrometers. DSC was performed on DSC-60 (Shimadzu).…”

Triplet sensitization enables bidirectional isomerization of diazocine with 130 nm redshift in excitation wavelengths

“…Diazocines also exhibit more efficient photoswitching using longer excitation wavelengths and possess higher quantum yields. [1][2][3][4][5][6][7][8][9][10][11][12][13] As a result, diazocines have found use in emerging elds, such as stimuli-responsive systems, [14][15][16][17][18][19] photoactuation, 20 and most notably, photopharmacology. [21][22][23][24][25][26][27][28] Unlike conventional azobenzene, whose triplet state properties have been investigated since the 1960s, 29 no studies on the triplet states of diazocine molecules have been published.…”

“…Diazocines also exhibit more efficient photoswitching using longer excitation wavelengths and possess higher quantum yields. 1–13 As a result, diazocines have found use in emerging fields, such as stimuli-responsive systems, 14–19 photoactuation, 20 and most notably, photopharmacology. 21–28…”