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Fatigue and photochromism S 1 excited state reactivity of diarylethenes from QTAIM and the stress tensor
Author(s) -
Yang Ping,
Xu Tianlv,
Momen Roya,
Azizi Alireza,
Kirk Steven R.,
Jenkins Samantha
Publication year - 2018
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25565
Subject(s) - photochromism , diarylethene , reactivity (psychology) , excited state , tensor (intrinsic definition) , realization (probability) , cauchy stress tensor , chemistry , isomerization , stress (linguistics) , computational chemistry , photochemistry , quantum mechanics , physics , organic chemistry , mathematics , pure mathematics , catalysis , medicine , philosophy , linguistics , alternative medicine , statistics , pathology
Abstract The realization of technologically relevant functional systems from idealized photochromic compounds remains elusive due to the double requirement that such switches must possess both highly efficient photo‐isomerization reactivity and extremely low fatigue over a large number of switching cycles. Nowadays, improvements of the switching properties in complex diarylethene structures are mainly attained on a “trial and error” basis through chemical substitutions aimed at tuning the chemical properties of the core of the diarylethene. Therefore, we present new guiding principles to analyze the first excited state reactivity of diarylethenes based on the quantum theory of atoms in molecules (QTAIM) including the stress tensor. This approach straightforwardly provides consistent theoretical justification to partner the already successful symmetric substitution patterns obtained from experiments. The guiding principles provided by QTAIM and stress tensor suggest more complex asymmetric patterns should be included for the systematic design of new technologically relevant functional compounds. The stress tensor trajectory T σ ( s ) analysis is used to characterize the photochromism reaction as reusable and the fatigue reaction as irreversible and find candidate sites for alteration by future experiment.