Solvent Dependence on Cooperative Vibrational Strong Coupling and Cavity Catalysis**

Strong light-matter coupling offers a unique way to control chemical reactions at the molecular level. Here, we compare the solvent effect on an ester solvolysis process under cooperative vibrational strong coupling (VSC). Three reactants, para-nitrophenylacetate, 3-methyl-para-nitrophenylbenzoate, and bis-(2, 4-dinitrophenyl) oxalate are chosen to study the effect of VSC on the solvolysis reaction rates. Two solvents, ethyl acetate and cyclopentanone, are also considered to compare the cavity catalysis by coupling the C=O stretching band of the reactant and the solvent molecules to a Fabry-Perot cavity mode. Interestingly, both solvents enhance the chemical reaction rate of para-nitrophenylacetate and 3-methyl-para-nitrophenylbenzoate under cooperative VSC conditions. However, the resonance effect is observed at different temperatures for different solvents, which is further confirmed by thermodynamic studies. Bis-(2, 4-dinitrophenyl) oxalate doesn′t respond to VSC in either of the solvent systems due to poor overlap of reactant and solvent C=O vibrational bands. Cavity detuning and other control experiments suggest that cooperative VSC of the solvent plays a crucial role in modifying the activation free-energy of the reaction. These findings, along with other observations, cement the concept of polaritonic chemistry.     

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

Here, we used an unconventional idea of cooperative vibrational strong coupling of solute and solvent molecules to enhance the rate of an esterification reaction. Different derivatives of p-nitrophenyl benzoate (solute) and isopropyl acetate (solvent) are cooperatively coupled to an infrared Fabry–Perot cavity mode. The apparent rates are increased by more than six times at the ON resonance condition, and the rate enhancement follows the lineshape of the vibrational envelope. Very interestingly, a strongly coupled system doesn''t obey the Hammett relations. Thermodynamics suggests that the reaction mechanism remains intact for cavity and non-cavity conditions. Temperature-dependent experiments show an entropy-driven process for the coupled molecules. Vacuum field coupling decreases the free energy of activation by 2–5 kJ mol⁻¹, supporting a catalysis process. The non-linear rate enhancement can be due to the reshuffling of the energy distribution between the substituents and the reaction center across the aromatic ring. These findings underline the non-equilibrium behavior of cavity catalysis.

Cavity catalysis: vibrational strong coupling of solute and solvent molecules enhanced the rate of an esterification reaction. Hammett relation breaks under strong light-matter coupling conditions suggesting its potential applications in catalysis.     

Autotuning of Vibrational Strong Coupling for Site-Selective Reactions

Site-selective chemistry opens new paths for the synthesis of technologically important molecules. When a reactant is placed inside a Fabry–Perot (FP) cavity, energy exchange between molecular vibrations and resonant cavity photons results in vibrational strong coupling (VSC). VSC has recently been implicated in modified chemical reactivity at specific reactive sites. However, as a reaction proceeds inside an FP cavity, the refractive index of the reaction solution changes, detuning the cavity mode away from the vibrational mode and weakening the VSC effect. Here we overcome this issue, developing actuatable FP cavities to allow automated tuning of cavity mode energy to maintain maximized VSC during a reaction. As an example, the site-selective reaction of the aldehyde over the ketone in 4-acetylbenzaldehyde is achieved by automated cavity tuning to maintain optimal VSC of the ketone carbonyl stretch during the reaction. A nearly 50 % improvement in site-selective reactivity is observed compared to an FP cavity with static mirrors, demonstrating the utility of actuatable FP cavities as microreactors for organic chemistry.     

Modification of Enzyme Activity by Vibrational Strong Coupling of Water

Vibrational strong coupling (VSC) has recently emerged as a completely new tool for influencing chemical reactivity. It harnesses electromagnetic vacuum fluctuations through the creation of hybrid states of light and matter, called polaritonic states, in an optical cavity resonant to a molecular absorption band. Here, we investigate the effect of vibrational strong coupling of water on the enzymatic activity of pepsin, where a water molecule is directly involved in the enzyme's chemical mechanism. We observe an approximately 4.5‐fold decrease of the apparent second‐order rate constant k_cat/K_m when coupling the water stretching vibration, whereas no effect was detected for the strong coupling of the bending vibration. The possibility of modifying enzymatic activity by coupling water demonstrates the potential of VSC as a new tool to study biochemical reactivity.     

Theoretical study on solvation effects in chemical reactions: A vibrational coupling model

A vibrational coupling model to treat the solvation effects in chemical reaction rate calculations is proposed and applied to the intramolecular hydrogen transfer reaction CH₃O· → ·CH₂OH in the condensed phase. The effect of solvation is taken into account in two ways: (1) the solvent effect on the activation energy of the reaction is simulated by including 39 surrounding water molecules, represented by fractional charges at the assumed atomic positions, in the potential energy surface calculation; and (2) the vibrational couplings between the 10 nearest solvent molecules and the molecules constituting the reaction system are explicitly included in a vibrational frequency calculation. RRKM theory with Miller's tunneling correction included is employed to calculate the rate constants. The effect of solvation causes a significant change in the chemical reaction rate, mainly through a lowering of the activation energy. The vibrational coupling causes a slight increase of the rate constant in the tunneling region by perturbing the vibrational frequencies of the reactant and transition states, which appear in the rate-constant expression, but has little effect at higher temperatures.     

Modulation of Prins Cyclization by Vibrational Strong Coupling

Light‐molecule strong coupling has emerged within the last decade as a new method to control chemical reactions. A few years ago it was discovered that chemical reactivity could be altered by vibrational strong coupling (VSC). Only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry, is investigated. A decrease of the second‐order rate constant with VSC of the reactant carbonyl stretching groups is observed. We also observe an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy, suggesting no substantive change in reaction pathway. The addition of common cycloaddition reactions to the stable of VSC‐modified chemical reactions is another step towards establishing VSC as a genuine tool for synthetic chemistry.     

Modulation of Prins Cyclization by Vibrational Strong Coupling

Light-molecule strong coupling has emerged within the last decade as a new method to control chemical reactions. A few years ago it was discovered that chemical reactivity could be altered by vibrational strong coupling (VSC). Only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry, is investigated. A decrease of the second-order rate constant with VSC of the reactant carbonyl stretching groups is observed. We also observe an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy, suggesting no substantive change in reaction pathway. The addition of common cycloaddition reactions to the stable of VSC-modified chemical reactions is another step towards establishing VSC as a genuine tool for synthetic chemistry.     

Isolable Silylene Ligands Can Boost Efficiencies and Selectivities in Metal‐Mediated Catalysis

A significant number of isolable silylenes are currently known. They have quickly developed from laboratory curiosities to useful ligands in metal‐mediated homogeneous catalysis. This includes their utilization in various catalytic transformations, such as C?C cross‐coupling, cyclotrimerization, hydroformylation, borylation, deuteration, hydrosilylation, amination, hydrogenation, and transfer semi‐hydrogenation reactions. Recent studies suggest that the silylene ligands surpass the steering properties of their phosphine and N‐heterocyclic carbene (NHC) analogues and provide excellent chemo‐, regio‐, and stereoselectivites. Mechanistic studies suggest that their promoted performance of metal‐mediated catalytic transformations results from a strong σ‐donor character along with cooperative effects of their Si^II centers. This Minireview covers the most recent advances in the field.     

On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge-Transfer Complexation

It is well known that symmetry plays a key role in chemical reactivity. Here we explore its role in vibrational strong coupling (VSC) for a charge-transfer (CT) complexation reaction. By studying the trimethylated-benzene–I₂ CT complex, we find that VSC induces large changes in the equilibrium constant K_DA of the CT complex, reflecting modifications in the ΔG° value of the reaction. Furthermore, by tuning the microfluidic cavity modes to the different IR vibrations of the trimethylated benzene, ΔG° either increases or decreases depending only on the symmetry of the normal mode that is coupled. This result reveals the critical role of symmetry in VSC and, in turn, provides an explanation for why the magnitude of chemical changes induced by VSC are much greater than the Rabi splitting, that is, the energy perturbation caused by VSC. These findings further confirm that VSC is powerful and versatile tool for the molecular sciences.     

Ground‐State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field

The ground‐state deprotection of a simple alkynylsilane is studied under vibrational strong coupling to the zero‐point fluctuations, or vacuum electromagnetic field, of a resonant IR microfluidic cavity. The reaction rate decreased by a factor of up to 5.5 when the Si?C vibrational stretching modes of the reactant were strongly coupled. The relative change in the reaction rate under strong coupling depends on the Rabi splitting energy. Product analysis by GC‐MS confirmed the kinetic results. Temperature dependence shows that the activation enthalpy and entropy change significantly, suggesting that the transition state is modified from an associative to a dissociative type. These findings show that vibrational strong coupling provides a powerful approach for modifying and controlling chemical landscapes and for understanding reaction mechanisms.     

On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge‐Transfer Complexation

It is well known that symmetry plays a key role in chemical reactivity. Here we explore its role in vibrational strong coupling (VSC) for a charge‐transfer (CT) complexation reaction. By studying the trimethylated‐benzene–I₂ CT complex, we find that VSC induces large changes in the equilibrium constant K_DA of the CT complex, reflecting modifications in the ΔG° value of the reaction. Furthermore, by tuning the microfluidic cavity modes to the different IR vibrations of the trimethylated benzene, ΔG° either increases or decreases depending only on the symmetry of the normal mode that is coupled. This result reveals the critical role of symmetry in VSC and, in turn, provides an explanation for why the magnitude of chemical changes induced by VSC are much greater than the Rabi splitting, that is, the energy perturbation caused by VSC. These findings further confirm that VSC is powerful and versatile tool for the molecular sciences.     

溶液反应机理与动力学-2：影响因素与动力学方程的一般形式

对引起溶液反应与气相反应速率差异的因素进行了分析。指出大量溶剂分子的存在,并不会导致反应物分子之间的碰撞频率大幅度降低。除影响反应物活度和起催化作用之外,溶剂化和微观粘度是影响溶液反应速率的主要因素。微观粘度的影响可正可负,可能存在"负粘度"效应。基于简单碰撞理论和过渡态理论,给出了溶液反应速率公式的一般形式,可以综合活化能和微观粘度的影响。该方法可以比较合理地解释一些实验现象。     

态-态热力学函数及其应用 I: 双分子交换反应

本文把Levine的态-态热力学函数由振动-振动态推广到振转-振转态, 对A+BC(v, j)→AB(v', j')+C双分子交换反应给出了Gibbs自由能△G^o(v, j→v',j', T)和化学平均常数K(v, j→v', j', T)在谐振子-截锥转子模型下的详细计算公式, 对H+O2(v, j)→HO(v', j')+O作了数值计算, 结果与由实验归纳出的定性规律相符合。利用本文给出的公式不仅可以对化学反应过程描述得更加细致和深刻, 而且可以方便地讨论分子的振动-转动态耦合对化学反应性的影响。     

para‐Selective C−H Borylation of (Hetero)Arenes by Cooperative Iridium/Aluminum Catalysis

para ‐Selective C−H borylation of benzamides and pyridines has been achieved by cooperative iridium/aluminum catalysis. A combination of iridium catalysts commonly employed for arene C−H borylation and bulky aluminum‐based Lewis acid catalysts provides an unprecedented strategy for controlling the regioselectivity of C−H borylation to give variously substituted (hetero)arylboronates, which are versatile synthetic intermediates for complex multi‐substituted aromatic compounds.     

Metal-Metal Cooperation in Dinucleating Complexes Involving Late Transition Metals Directed towards Organic Catalysis

Cooperatively bimetallic organic catalysis,coupling actions of two metal centers in a catalytic organic transformation via co-activation of a single molecule or synergistic activation of two molecules,has witnessed rapid development in the last decades.     

Selective crystallization via vibrational strong coupling

The coupling of (photo)chemical processes to optical cavity vacuum fields is an emerging method for modulating molecular and material properties. Recent reports have shown that strong coupling of the vibrational modes of solvents to cavity vacuum fields can influence the chemical reaction kinetics of dissolved solutes. This suggests that vibrational strong coupling might also effect other important solution-based processes, such as crystallization from solution. Here we test this hitherto unexplored notion, investigating pseudopolymorphism in the crystallization from water of ZIF metal–organic frameworks inside optical microcavities. We find that ZIF-8 crystals are selectively obtained from solution inside optical microcavities, where the OH stretching vibration of water is strongly coupled to cavity vacuum fields, whereas mixtures of ZIF-8 and ZIF-L are obtained otherwise. Moreover, ZIF crystallization is accelerated by solvent vibrational strong coupling. This work suggests that cavity vacuum fields might become a tool for materials synthesis, biasing molecular self-assembly and driving macroscopic material outcomes.

Strong coupling of optical cavity vacuum fields and solvent vibrations leads to selective crystallization in a pseudo-polymorphic MOF system.     

Enantioselective C?H Bond Functionalization Triggered by Radical Trifluoromethylation of Unactivated Alkene

An asymmetric unactivated alkene/C H bond difunctionalization reaction for the concomitant construction of C CF₃ and C O bonds was realized by using a Cu/Brønsted acid cooperative catalytic system, thus providing facile access to valuable chiral CF₃‐containing N,O‐aminals with excellent regio‐, chemo‐, and enantioselectivity. Mechanistic studies revealed that this reaction may proceed by an unprecedented 1,5‐hydride shift involving activation of unactivated alkenes and a radical trifluoromethylation to initiate subsequent enantioselective functionalization of C H bonds. Control experiments also suggested that chiral Brønsted acid plays multiple roles and not only controls the stereoselectivity but also increases the reaction rate through activation of Togni’s reagent.     

Long‐Distance Rate Acceleration by Bulk Gold

We report on a very unusual case of surface catalysis involving azobenzenes in contact with a Au(111) surface. A rate acceleration of the cis–trans isomerization on gold up to a factor of 1300 compared to solution is observed. By using carefully designed molecular frameworks, the electronic coupling to the surface can be systematically tuned. The isomerization kinetics of molecules with very weak coupling to the metal is similar to that found in solution. For their counterparts with strong coupling, the relaxation rate is shown to depend on the spin‐density distribution in the triplet states of the molecules. This suggests that an intersystem crossing is involved in the relaxation process. Aside from their impact on catalytic processes, these effects could be used to trigger reactions over long distances.     

Infrared spectra of a model phenol-amine proton transfer complex in nanoconfined CH3Cl

The vibrational spectra of a model phenol-amine proton transfer complex dissolved in CH3Cl solvent confined in a 12 A radius spherical hydrophobic cavity were calculated using mixed quantum-classical molecular dynamics simulations. The reaction free energy of the proton transfer complex was varied in order to explore the contributions to the vibrational absorption band from product and reactant species. The vibrational spectra of the model proton transfer complex resulted in motionally narrowed spectral linewidths with two distinct peaks for products and reactants in cases where the system undergoes chemical exchange. It was found that the n=1 and n=2 vibrational excited states combine to form diabatic states such that the spectra have contributions from both n=0 --> n=1 and n=0 --> n=2 transitions. A strong relationship between the instantaneous vibrational frequency and a collective solvent coordinate was found that assists in understanding the origin of the spectral features.