2199-54-4Relevant articles and documents
-
Ochiai,Tsuda,Ikuma
, p. 1713 (1936)
-
Tuning azoheteroarene photoswitch performance through heteroaryl design
Calbo, Joaquín,Weston, Claire E.,White, Andrew J. P.,Rzepa, Henry S.,Contreras-García, Julia,Fuchter, Matthew J.
supporting information, p. 1261 - 1274 (2017/05/15)
Photoswitchable compounds, which can be reversibly switched between two isomers by light, continue to attract significant attention for a wide array of applications. Azoheteroarenes represent a relatively new but understudied type of photoswitch, where one of the aryl rings from the conventional azobenzene class has been replaced with a fivemembered heteroaromatic ring. Initial studies have suggested the azoheteroarenes-the arylazopyrazoles in particular- to have excellent photoswitching properties (quantitative switching and long Z isomer half-life). Here we present a systematic computational and experimental study to elucidate the origin of the long thermal half-lives and excellent addressability of the arylazopyrazoles, and apply this understanding to determine important structure-property relationships for a wide array of comparable azoheteroaryl photoswitches. We identify compounds with Z isomer half-lives ranging from seconds to hours, to days and to years, and variable absorption characteristics, all through tuning of the heteraromatic ring. Conformation perhaps plays the largest role in determining such properties: the compounds with the longest isomerization half-lives adopt a T-shaped ground state Z isomer conformation and proceed through a T-shaped isomerization pathway, whereas the most complete photoswitching is achieved for compounds that have a twisted (rather than T-shaped) Z isomer conformation. By balancing these factors, we report a new azopyrazole 3pzH, which can be quantitatively switched to its Z isomer (1/2 = 74 d at 25 °C). Given the large tunability of their properties, the predictive nature of their performance, and the other functional opportunities afforded by usage of a heteroaromatic system, we believe the azoheteroaryl photoswitches to have huge potential in a wide range of optically addressable applications.
Synthesis and physicochemical properties of hydrobromides of alkyl-substituted dipyrrolylmethenes
Berezin,Semeikin,Antina,Pashanova,Lehedeva,Bukushina
, p. 1949 - 1955 (2007/10/03)
Hydrobromides of [(alkylpyrrol-2(1H)-ylidenio)methyl]pyrroles (α,α-dipyrrolylmethenes) and of their α,β and β,β isomers were prepared, and their resistance to oxidative thermal degradation was studied. The solvation properties of these compounds in various organic solvents were examined spectrophotometrically and calorimetrically.
