title: Tuning Azoheteroarene Photoswitch Performance through Heteroaryl Design.
abstract: 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 five-membered 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 (>98%) with 355 nm irradiation, near-quantitatively (97%) switched back to the E isomer with 532 nm irradiation, and has a very long half-life for thermal isomerization (t1/2= 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.
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia , 46890 Paterna, Spain.
authors.forename: Joaquín
authors.initials: J
authors.lastname: Calbo
authors.affiliation: Department of Chemistry, Imperial College London , London SW7 2AZ, United Kingdom.
authors.forename: Claire E
authors.initials: CE
authors.lastname: Weston
authors.affiliation: Department of Chemistry, Imperial College London , London SW7 2AZ, United Kingdom.
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
authors.affiliation: Department of Chemistry, Imperial College London , London SW7 2AZ, United Kingdom.
authors.forename: Henry S
authors.initials: HS
authors.lastname: Rzepa
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06, CNRS , Laboratoire de Chimie Théorique, CC 137 - 4, place Jussieu, F-75252 Paris Cedex 05, France.|CNRS, UMR 7616, LCT , F-75005 Paris, France.
authors.forename: Julia
authors.initials: J
authors.lastname: Contreras-García
authors.affiliation: Department of Chemistry, Imperial College London , London SW7 2AZ, United Kingdom.
authors.forename: Matthew J
authors.identifier: 0000-0002-1767-7072
authors.initials: MJ
authors.lastname: Fuchter