The working mechanism of a series of multi-responsive molecular switches has been investigated at atomistic level by using density functional theory (DFT) and its time dependent formulation (TDDFT). The keto-enol tautomerization has been explored considering the base assisted process, which can easily occur with a low activation energy, and also evaluating the feasibility of the electrically generation of the colored enolate form proposed in literature. Our data show that the electrically induced mechanism, consisting of a reduction followed by a proton transfer, is thermodynamically unfavorable, while a concerted proton coupled electron transfer process (PCET) can be proposed as working mechanism, resulting exergonic and able to better combine theoretical and experimental evidences.
Photophysical properties of methyl ketone based multi-responsive electrochromic materials: A theoretical investigation
Alberto M. E.Investigation
;De Simone B. C.Investigation
;Marino T.Supervision
;Russo N.
Writing – Review & Editing
;Toscano M.Supervision
2021-01-01
Abstract
The working mechanism of a series of multi-responsive molecular switches has been investigated at atomistic level by using density functional theory (DFT) and its time dependent formulation (TDDFT). The keto-enol tautomerization has been explored considering the base assisted process, which can easily occur with a low activation energy, and also evaluating the feasibility of the electrically generation of the colored enolate form proposed in literature. Our data show that the electrically induced mechanism, consisting of a reduction followed by a proton transfer, is thermodynamically unfavorable, while a concerted proton coupled electron transfer process (PCET) can be proposed as working mechanism, resulting exergonic and able to better combine theoretical and experimental evidences.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
