Excited‐State Intramolecular Proton Transfer: Photoswitching in Salicylidene Methylamine Derivatives

Abstract

The effect of chemical substitutions on the photophysical properties of the salicylidene methylamine molecule (SMA) (J. Jankowska, M. F. Rode, J. Sadlej, A. L. Sobolewski, ChemPhysChem, 2012, 13, 4287-4294) is studied with the aid of ab initio electronic structure methods. It is shown that combining π-electron-donating and π-electron-withdrawing substituents results in an electron-density push-and-pull effect on the energetic landscape of the ground and the lowest excited ππ* and nπ* singlet states of the system. The presented search for the most appropriate SMA derivatives with respect to their photoswitching functionality offers an efficient prescreening tool for finding chemical structures before real synthetic realization.

Tailoring the Schiff base photoswitching – a non-adiabatic molecular dynamics study of substituent effect on excited state proton transfer

“…The static results discussed in this part of the study stay in good agreement with ADC(2)/cc-pVDZ fully relaxed PE surface exploration reported in ref. 63 .…”

Structural Correlations between Luminescent Properties and Excited State Internal Proton Transfer in Some Zinc(II) N,N′-Bis(salicylidenes)

“…40 Some of these ligands might also undergone excited-state intramolecular proton transfer (ESIPT). [41][42][43][44][45][46][47][48] This process involves a keto (K * ) ↔enol (E * ) balance in the electronic excited state of molecules containing intramolecular H-bonds. 49,50 The electronic absorption of energy by N,N'-bis(salicylidenes) in the ground state leads to an excited electronic state in the enol form.…”

Photophysical properties of betaxanthins: miraxanthin V – insight into the excited-state deactivation mechanism from experiment and computations

“…This effect was detected in a series of derivatives of 7-hydroxy-quinoline (7HQ) 47 and salicylidene methylamine. 49 Thus, a hindered rotation around a nominally double bond in the S 0 state may become allowed in the S 1 -excited state due to lowering of the barrier, explained by this bond becoming a longer and weaker (single) bond in the S 1 state.…”