Abstract
Molecular switches are molecules that can reversibly be shifted between at least two stable states with different physical and chemical properties, making them interesting for application as chemical sensors or molecular machines. We recently discovered that five-membered, cyclic biradicals based on group 15 elements are efficient and robust photochemical switches that can be activated by red light. The quantum yield of the photo-isomerization is as high as 24.6%, and the thermal equilibration of the photo-activation product proceeds rapidly at ambient temperature. The fully reversible process was studied by experimental and high-level ab initio techniques. We could further demonstrate that the biradical character could be completely turned on and off, so the system could be applied to control chemical equilibria that involve activation products of the cyclic biradicals.
Highlights
The term “molecular switch” originated in the early 1980s and was rst used in conjunction with biological signal transmission.[1]
We recently discovered that five-membered, cyclic biradicals based on group 15 elements are efficient and robust photochemical switches that can be activated by red light
We could further demonstrate that the biradical character could be completely turned on and off, so the system could be applied to control chemical equilibria that involve activation products of the cyclic biradicals
Summary
The term “molecular switch” originated in the early 1980s and was rst used in conjunction with biological signal transmission.[1]. Interconversion can be induced by external stimuli such as temperature, chemical modi cations, redox reactions, electric elds, or irradiation with photons.[2,3,4,5] The most commonly known type of molecular switches are pH indicators, which are based on acid–base equilibria and belong to the group of chemically activated compounds.[6,7] Other chemically switchable systems may, for example, nd application in the eld of gas or ion sensing,[5,8] or be used as redox indicators.[7]. Light-activated molecular switches promise diverse applications, e.g. as photoactuators[9,10,11] or photoregulated catalysts.[12,13] a growing research interest is aimed both at the synthesis of new systems as well as the Understanding bond formation and breaking processes (or the nature of chemical bonds in general) has been a widely
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