Abstract:In this letter, we propose a novel, ultrafast, efficient molecular switch whose switching mechanism involves the electric field-driven intramolecular proton transfer. By means of ab initio quantum chemical calculations and on-the-fly dynamics simulations, we examine the switching performance of an isolated salicylidene aniline molecule and analyze the perspectives of its possible use as an electric field-controlled molecular electronics unit.
“…Since the discovery of the phenomenon in methylsalicylate by Weller in 1956, 15 and the realistic interpretation by Otterstedt 16 and Kasha, 17 many investigations have been reported. A non exhaustive list of studies includes works focussed on salicylic acid, 18 – 22 methyl salicylate, 23 – 28 salicylideneaniline, 29 – 32 hydroxy-acetophenones, 26 , 28 , 33 hydroxy-indanone, 20 – 22 , 26 hydroxy flavones, 17 , 34 – 41 (pyridyl)-pyrroles, -pyrazoles and -indoles, 42 – 49 fluorescent protein chromogens, 50 , 51 hydroxy-benzofluorenone, 52 phenyl-phenol, 53 hydroxyphenyl-oxazole (HO), 28 hydroxyphenyl-benzoxazoles (HBO), 54 – 69 hydroxybenzofuran-benzoxazoles (HBBO), 70 hydroxyphenyl-benzothiazole (HBT) 54 , 61 , 62 , 71 – 80 and hydroxyphenyl-benzimidazoles (HBI). 56 , 60 – 62 , 77 , 81 – 88 The typical HBO and HBI structures, two of the most popular ESIPT cores, are displayed in Fig.…”
“…Since the discovery of the phenomenon in methylsalicylate by Weller in 1956, 15 and the realistic interpretation by Otterstedt 16 and Kasha, 17 many investigations have been reported. A non exhaustive list of studies includes works focussed on salicylic acid, 18 – 22 methyl salicylate, 23 – 28 salicylideneaniline, 29 – 32 hydroxy-acetophenones, 26 , 28 , 33 hydroxy-indanone, 20 – 22 , 26 hydroxy flavones, 17 , 34 – 41 (pyridyl)-pyrroles, -pyrazoles and -indoles, 42 – 49 fluorescent protein chromogens, 50 , 51 hydroxy-benzofluorenone, 52 phenyl-phenol, 53 hydroxyphenyl-oxazole (HO), 28 hydroxyphenyl-benzoxazoles (HBO), 54 – 69 hydroxybenzofuran-benzoxazoles (HBBO), 70 hydroxyphenyl-benzothiazole (HBT) 54 , 61 , 62 , 71 – 80 and hydroxyphenyl-benzimidazoles (HBI). 56 , 60 – 62 , 77 , 81 – 88 The typical HBO and HBI structures, two of the most popular ESIPT cores, are displayed in Fig.…”
“…10 We have found an example of a reversible switch triggered by the EF of proton-transfer in salicylidene aniline, the report of which was published recently. 21 Investigations of molecular switches were prompted by expectations of them serving as circuit elements in molecular electronics and hence the rate of the switching process has also been investigated in systems that display switching properties. 12,13,21 These, and other molecular electronic devices, however, will probably be replaced by robust crystalline extended devices.…”
The effect of a homogeneous static electric field on the Li-benzene complex in two configurations, one with a larger Li-C6H6 distance ("loose") and one with a shorter distance ("tight"), has been investigated. The electric field has the same orientation as the direction of the dipole moments of the complexes. When the direction of the field intensity vector was the same as that of the dipole moment vector, optimization of the complex's geometry in one configuration resulted in switching it to the other one. Reversing the direction of the field then transformed the other configuration back to the original one. This switching behavior was observed beginning with the loose configuration and with the tight configuration. The geometrical and electronic parameters of the complex after four steps of the reversible switching have been calculated for a selected field intensity of 0.005 atomic units (a.u.), that is 0.257 V Å(-1).
“…In the first model case, we studied tautomeric enol-keto or keto-enol rearrangements within salicydene aniline, a model system representing a larger class of molecular switches [ 2 ]. These switches have become a “hot-topic” thanks to their potential application in molecular electronics, data storage and processing devices.…”
Section: Resultsmentioning
confidence: 99%
“…In the following report, we have examined two model systems, where catalytic fields, ∆ s , have been confronted with changes of the activation energy resulting from the substitution of hydrogen by fluorine. In the first model system, a proton transfer in salicydene aniline [ 2 ] has been considered (Scheme 1 ): Scheme 1 Proton transfer in salicydene aniline …”
Catalytic fields illustrate topology of the optimal charge distribution of a molecular environment reducing the activation energy for any process involving barrier crossing, like chemical reaction, bond rotation etc. Until now, this technique has been successfully applied to predict catalytic effects resulting from intermolecular interactions with individual water molecules constituting the first hydration shell, aminoacid mutations in enzymes or Si→Al substitutions in zeolites. In this contribution, hydrogen to fluorine (H→F) substitution effects for two model reactions have been examined indicating qualitative applicability of the catalytic field concept in the case of systems involving intramolecular interactions.
Graphical abstractHydrogen to fluorine (H→F) substitution effects on activation energy in [kcal/mol]
Electronic supplementary materialThe online version of this article (10.1007/s00894-017-3559-6) contains supplementary material, which is available to authorized users.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
