Photomechanochemical control over stereoselectivity in the [2 + 2] photodimerization of acenaphthylene

Biswas, Sankarsan; Banerjee, Sayan; Shlain, Milan A.; Bardin, A. A.; Ulijn, Rein V.; Nannenga, Brent L.; Rappe, Andrew M.; Braunschweig, Adam B.

doi:10.1039/d2fd00122e

Cited by 13 publications

(13 citation statements)

References 54 publications

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“…These results also explain that the large Δ V ‡ for mechanochemical reactions occur as a result of the proximity to surfaces and uniaxial stress that cause molecular distortion. This distortion lowers the reaction energy and drives the reaction through a distinct reaction trajectory, which explains why different isomers are often obtained under F than in solvent ( 9 , 55 ). This phenomenon—the distortion of molecules near surfaces that occurs under F to lower Δ G ‡ —will be relatively independent of molecular structure and suggests that mechanochemical reactivity is more widespread than previously anticipated.…”

Section: Modeling Mechanical Distortionmentioning

confidence: 99%

Acceleration of Diels-Alder reactions by mechanical distortion

Zholdassov

Liu

Garcia

et al. 2023

Science

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Challenges in quantifying how force affects bond formation have hindered the widespread adoption of mechanochemistry. We used parallel tip-based methods to determine reaction rates, activation energies, and activation volumes of force-accelerated [4+2] Diels-Alder cycloadditions between surface-immobilized anthracene and four dienophiles that differ in electronic and steric demand. The rate dependences on pressure were unexpectedly strong, and substantial differences were observed between the dienophiles. Multiscale modeling demonstrated that in proximity to a surface, mechanochemical trajectories ensued that were distinct from those observed solvothermally or under hydrostatic pressure. These results provide a framework for anticipating how experimental geometry, molecular confinement, and directed force contribute to mechanochemical kinetics.

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Section: Modeling Mechanical Distortionmentioning

confidence: 99%

Acceleration of Diels-Alder reactions by mechanical distortion

Zholdassov

Liu

Garcia

et al. 2023

Science

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“…For reactions other than decomposition, such as synthesis, or exchange, it is significantly more difficult to suggest how a mechanical pulse can be transformed into chemical changes. Among research groups that are developing first-principles methods to study force- and stress-enabled mechanochemistry and consider the processes in the mechanical stress field at the molecular level for non-decomposition processes, such as reaction of graphene with selected organic molecules, or stereoselective photodimerization, one can mention research by A. Rappe et al 331,332…”

Section: Achievementsmentioning

confidence: 99%

Spiers Memorial Lecture: Mechanochemistry, tribochemistry, mechanical alloying – retrospect, achievements and challenges

Boldyreva

2023

Faraday Discuss.

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“…Figure 1A). [17][18][19][20][21][22][23][24][25][26][27] This is mainly due to the lack of suitable equipment. Photoreactors and ball mills are inherently difficult to combine since the milling vessels commonly used are impermeable to light.…”

Section: Introductionmentioning

confidence: 99%

The Regioselective Solid‐State Photo‐Mechanochemical Synthesis of Nanographenes with UV light

et al. 2023

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Photochemical reactors inherently suffer from the low penetration depth of light and therefore rely on high dilutions to enable chemical reactions. Here we present the first method of UV (ultraviolet) photochemistry in the complete absence of bulk solvents in a ball mill. Triphenylene was synthesized by two routes, the Mallory reaction and the cyclodehydrochlorination (CDHC), resulting in yields of 81 and 92 %, respectively. The reaction was successfully scaled up to the gram scale and the robustness of the method was demonstrated for several different substrates. Finally, the regioselective assembly of nanographenes by mechanochemistry was demonstrated for larger systems. Thus, the mechanochemical approach presented here provides a powerful new tool for the atomically precise construction of nanographenes.

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Photomechanochemical control over stereoselectivity in the [2 + 2] photodimerization of acenaphthylene

Abstract: Tuning solubility and mechanical activation alters the stereoselectivity of the [2+2] photochemical cycloaddition of acenaphthylene. Photomechanochemical conditions produce the syn cyclobutane, whereas the solid-state reaction in the absence of mechanical...

Cited by 13 publications

References 54 publications

Acceleration of Diels-Alder reactions by mechanical distortion

Acceleration of Diels-Alder reactions by mechanical distortion

Spiers Memorial Lecture: Mechanochemistry, tribochemistry, mechanical alloying – retrospect, achievements and challenges

The Regioselective Solid‐State Photo‐Mechanochemical Synthesis of Nanographenes with UV light

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