Stilbenes Revisited: Understanding the Mechanism of Mechanochemical Coupling

O’Neill, Robert T.; Boulatov, Roman

doi:10.1002/9783527827626.ch12

Cited by 3 publications

(2 citation statements)

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“…In a few photoswitch motives, both aspects can be combined, for example, in spiropyrans, [6][7][8] Stenhouse dyes, 9,10 or the recently discovered hemithioindigo (HTI)-TOND motive. 11 Photoinduced double bond isomerization has been utilized for a long time with, e.g., stilbene [12][13][14] and azobenzene chromophores, 15 however additional substitutions are needed to shi their absorptions to the visible part of the spectrum. [16][17][18][19][20][21][22] Indigoid chromophores have gained traction as intrinsically visible light responsive photoswitches for double bond isomerization reactions.…”

Section: Introductionmentioning

confidence: 99%

“…11 Photoinduced double bond isomerization has been utilized for a long time with, e.g. , stilbene 12–14 and azobenzene chromophores, 15 however additional substitutions are needed to shift their absorptions to the visible part of the spectrum. 16–22 Indigoid chromophores have gained traction as intrinsically visible light responsive photoswitches for double bond isomerization reactions.…”

Section: Introductionmentioning

confidence: 99%

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A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches

2023

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches

2023

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Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis

Yu,

O’Neill,

Boulatov

et al. 2023

Nat Commun

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Allosteric control of reaction thermodynamics is well understood, but the mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplored. Here we report a molecular scaffold in which the rate of thermal E-to-Z isomerization of an alkene increases by a factor of as much as 104 in response to fast binding of a metal ion to a remote receptor site. A mechanochemical model of the olefin coupled to a compressive harmonic spring reproduces the observed acceleration quantitatively, adding the studied isomerization to the very few reactions demonstrated to be sensitive to extrinsic compressive force. The work validates experimentally the generalization of mechanochemical kinetics to compressive loads and demonstrates that the formalism of force-coupled reactivity offers a productive framework for the quantitative analysis of the molecular basis of allosteric control of reaction kinetics. Important differences in the effects of compressive vs. tensile force on the kinetic stabilities of molecules are discussed.

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Experimental quantitation of molecular conditions responsible for flow-induced polymer mechanochemistry

O’Neill

Boulatov

2023

Nat. Chem.

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Stilbenes Revisited: Understanding the Mechanism of Mechanochemical Coupling

Cited by 3 publications

References 83 publications

A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches

A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches

Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis

Experimental quantitation of molecular conditions responsible for flow-induced polymer mechanochemistry

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