Shuttling Motion in a Host–Guest Complex Triggered by Spiropyran to Merocyanine Reversible Chemical Transformation

Hernández-Melo, Denhy; Cervantes, Ruy; Tiburcio, Jorge

doi:10.1021/acs.joc.7b00509

Cited by 8 publications

(2 citation statements)

References 27 publications

(21 reference statements)

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“…This behaviour parallels with host-guest chemistry.H owever,i t involves formation of am echanical bond by the reversible slippage of ac yclic moleculeo nto al inear one. Rate of reversible slippage of the macrocycle in 136 was quantifiedb yT iburcio and co-workers, [212] with 1 H-1 HR OESY exchange measurements giving k ex = 1.3 s À1 (Scheme 42).…”

Section: Ring Opening/closurementioning

confidence: 99%

Mechanisms and Beyond: Elucidation of Fluxional Dynamics by Exchange NMR Spectroscopy

Nikitin

O'Gara

2019

Chemistry A European J

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Detailed mechanistic information is crucial to our understanding of reaction pathways and selectivity. Dynamic exchange NMR techniques, in particular 2D exchange spectroscopy (EXSY) and its modifications, provide indispensable intricate information on the mechanisms of organic and inorganic reactions and other phenomena, for example, the dynamics of interfacial processes. In this Review, key results from exchange NMR studies of small molecules over the last few decades are systemised and discussed. After a brief introduction to the theory, the key types of dynamic processes are identified and fundamental examples given of intra‐ and intermolecular reactions, which, in turn, could involve, or not, bond‐making and bond‐breaking events. Following that logic, internal molecular rotation, intramolecular stereomutation and molecular recognition will first be considered because they do not typically involve bond breaking. Then, rearrangements, substitution‐type reactions, cyclisations, additions and other processes affecting chemical bonds will be discussed. Finally, interfacial molecular dynamics and unexpected combinations of different types of fluxional processes will also be highlighted. How exchange NMR spectroscopy helps to identify conformational changes, coordination and molecular recognition processes as well as quantify reaction energy barriers and extract detailed mechanistic information by using reaction rate theory in conjunction with computational techniques will be shown.

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Section: Ring Opening/closurementioning

confidence: 99%

Mechanisms and Beyond: Elucidation of Fluxional Dynamics by Exchange NMR Spectroscopy

Nikitin

O'Gara

2019

Chemistry A European J

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“…In order to construct a photoresponsive molecular switch or machine, photoactive molecules such as azobenzenes, alkenes, spiropyrans, and others have to be incorporated into the structures, often requiring tedious synthesis. In 2007, Credi and co-workers reported that an acid/base responsive pseudorotaxane based on calix[6]arene and bipyridinium can be photoswitched by coupling to a photoacid through intermolecular proton transfer.…”

mentioning

confidence: 99%

Light-Controlled Switching of a Non-photoresponsive Molecular Shuttle

et al. 2017

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Photoswitchable Host‐Guest Systems Incorporating Hemithioindigo and Spiropyran Units

Moncelsi

Ballester

2019

ChemPhotoChem

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We cover selected examples of the incorporation of hemithioindigo and spiropyran units in one of the binding partners of synthetic host‐guest systems. In the simplest systems, the isomerization of the switch simply modulates the thermodynamic stability of the resulting isomeric host‐guest complexes. The presence of more than two binding partners constitute multicomponent host‐guest systems. In some of them, the isomerization of the molecular switch alters the composition of the system producing a shuttling process of one of the components between different hosts. In others, the isomerization process controls the uptake and release of some of the components from/to the bulk solution. We show that the understanding of the isomerization mechanisms of the molecular switches and the effects produced by the external stimuli are essential for the design of complex and responsive supramolecular host‐guest systems. The physicochemical properties of the hemithioindigo and spiropyran molecular photoswitches are complementary, providing different avenues to their applications in solution and material science.

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Shuttling Motion in a Host–Guest Complex Triggered by Spiropyran to Merocyanine Reversible Chemical Transformation

Cited by 8 publications

References 27 publications

Mechanisms and Beyond: Elucidation of Fluxional Dynamics by Exchange NMR Spectroscopy

Mechanisms and Beyond: Elucidation of Fluxional Dynamics by Exchange NMR Spectroscopy

Light-Controlled Switching of a Non-photoresponsive Molecular Shuttle

Photoswitchable Host‐Guest Systems Incorporating Hemithioindigo and Spiropyran Units

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