Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling

Abstract

Vibrational strong coupling (VSC) has recently been shown to change the rate and chemoselectivity of ground‐state chemical reactions via the formation of light–matter hybrid polaritonic states. However, the observation that vibrational‐mode symmetry has a large influence on charge‐transfer reactions under VSC suggests that symmetry considerations could be used to control other types of chemical selectivity through VSC. Here, we show that VSC influences the stereoselectivity of the thermal electrocyclic ring opening of a cyclobutene derivative, a reaction which follows the Woodward–Hoffmann rules. The direction of the change in stereoselectivity depends on the vibrational mode that is coupled, as do changes in rate and reaction thermodynamics. These results on pericyclic reactions confirm that symmetry plays a key role in chemistry under VSC.

Cavity catalysis: modifying linear free-energy relationship under cooperative vibrational strong coupling

“… 38 Another interesting work is to see the breaking of the Woodward–Hoffmann rule and the modification of stereoselectivity under VSC. 39 We have recently shown that cooperative VSC of solute to solvent molecules can drastically modify the chemical reaction rate. 40 A similar approach was also used to control enzyme hydrolysis by coupling to water molecules.…”

Vibrational Coupling of Water from Weak to Ultrastrong Coupling Regime via Cavity Mode Tuning

“…In contrast, in the case of the strong coupling regime, the photon can mediate hybridization of the electromagnetic field to achieve energy splitting of polaritonic states. ,, As a result, observed Rabi splitting frequency is larger value than sum of photon loss rate and dephasing rate. Recently, polaritonic states have been used to transform ground-state molecular properties via formation of a vacuum strong coupling state. − This concept can also be applied to the vibrational states of molecules; placing molecules in a microscale cavity induces the vibro-polaritonic states, − which leads to modification of the ground-state thermochemical reactivity via vacuum vibrational coupling. − This vacuum vibrational strong coupling is also used to modify Raman scattering, , vibro-polaritonic infrared (IR) emissions, the self-assembly of molecules, , ferromagnetism, and even the superconductivity of materials . Recently, we also investigated the use of vacuum vibrational coupling to modify the proton conductivity of aqueous electrolyte solutions .…”

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling

“…In the last several years, it has been shown that coupling vibrational modes in this way has a pronounced effect on chemistry and molecular properties. [3,[5][6][7][8][9][10][11][12][13][14][15][16][17]20] In this vibrational strong coupling regime (VSC), vibro-polaritonic states (VP + , VPÀ) are formed, separated by the so-called Rabi splitting energy (" h W R ) (Figure 1 a). In typical experiments, a large number N of molecules are coupled by VSC to a single optical mode which leads to the formation of N-1 dark states (DS) which are, together with VP + and VPÀ, delocalized over many molecules.…”