title: Towards thermally stable cyclophanediene-dihydropyrene photoswitches.
abstract: Cyclophanediene dihydropyrenes (CPD-DHP) are photochromic compounds because they change their color by irradiation with lights of different color. Potential use of CPD-DHP photoswitch in memory devices requires a very slow thermal return in the dark in the absence of any side reaction. Herein, thermal return of CPDs to DHPs, and an unwanted sigmatropic shift in DHP is studied through density functional theory calculations at (U)B3LYP/6-31+G(d). The thermal return occurs through symmetry forbidden conrotatory electrocyclic reaction. Dimethyl amino CPD-DHP photoswitch pair has the highest activation barrier for electrocyclization and sigmatropic shifts. The lowest activation barrier for symmetry forbidden electrocyclization is observed for GeBr3 functionalized CPD. An unprecedented decomposition pathway involving elimination of the internal substituents is predicted for Cl, Br and SMe functionalized DHPs. This study shows great promise in understanding the Woodward Hoffmann forbidden processes and, in reducing the synthetic efforts toward robust photochromes for memory applications.
authors.affiliation: Department of Chemistry, COMSATS Institute of Information Technology, Abbottabad, Pakistan, 22060.
authors.forename: Nasir
authors.initials: N
authors.lastname: Khan
authors.forename: Nadeem S
authors.initials: NS
authors.lastname: Sheikh
authors.forename: Ather F
authors.initials: AF
authors.lastname: Khan
authors.forename: Ralf
authors.initials: R
authors.lastname: Ludwig
authors.forename: Tariq
authors.initials: T
authors.lastname: Mahmood
authors.forename: Wajid
authors.initials: W
authors.lastname: Rehman
authors.forename: Yasair S S
authors.initials: YS
authors.lastname: Al-Faiyz
authors.forename: Khurshid
authors.initials: K
authors.lastname: Ayub
mesh_terms: D008956:Models, Chemical; D008958:Models, Molecular; D010777:Photochemistry; D013237:Stereoisomerism; D013816:Thermodynamics