Control Of Chemical Reactivity Research Articles

Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes

Nanoscale control of chemical reactivity, manipulation of reaction pathways, and ultimately driving the outcome of chemical reactions are quickly becoming reality. A variety of tools are concurring to establish such capability. The confinement of guest molecules inside nanoreactors, such as the hollow nanostructures of carbon nanotubes (CNTs), is a straightforward and highly fascinating approach. It mechanically hinders some molecular movements but also decreases the free energy of translation of the system with respect to that of a macroscopic solution. Here, we examined, at the quantum mechanics/molecular mechanics (QM/MM) level, the effect of confinement inside CNTs on nucleophilic substitution (SN2) and elimination (syn-E2 and anti-E2) using as a model system the reaction between ethyl chloride and chloride. Our results show that the three reaction mechanisms are kinetically and thermodynamically affected by the CNT host. The size of the nanoreactor, i.e., the CNT diameter, represents the key factor to control the energy profiles of the reactions. A careful analysis of the interactions between the CNTs and the reactive system allowed us to identify the driving force of the catalytic process. The electrostatic term controls the reaction kinetics in the SN2 and syn/anti-E2 reactions. The van der Waals interactions play an important role in the stabilization of the product of the elimination process.

Gradient area-selective deposition for seamless gap-filling in 3D nanostructures through surface chemical reactivity control

The integration of bottom-up fabrication techniques and top-down methods can overcome current limits in nanofabrication. For such integration, we propose a gradient area-selective deposition using atomic layer deposition to overcome the inherent limitation of 3D nanofabrication and demonstrate the applicability of the proposed method toward large-scale production of materials. Cp(CH3)5Ti(OMe)3 is used as a molecular surface inhibitor to prevent the growth of TiO2 film in the next atomic layer deposition process. Cp(CH3)5Ti(OMe)3 adsorption was controlled gradually in a 3D nanoscale hole to achieve gradient TiO2 growth. This resulted in the formation of perfectly seamless TiO2 films with a high-aspect-ratio hole structure. The experimental results were consistent with theoretical calculations based on density functional theory, Monte Carlo simulation, and the Johnson-Mehl-Avrami-Kolmogorov model. Since the gradient area-selective deposition TiO2 film formation is based on the fundamentals of molecular chemical and physical behaviours, this approach can be applied to other material systems in atomic layer deposition.

Spectral response of vibrational polaritons in an optomechanical cavity

Vibrational strong coupling provides a convenient way to modify the energy of molecular vibrations and to explore the control of chemical reactivity. In this work, we theoretically report the various vibrational anharmonicities that modulate the dynamics of optomechanically coupled W(CO)6-cavity. The optomechanical free-space cavity consists of movable photonic crystal membrane, which creates photonic bound states to interact with the molecular vibration. This coupled system is used for realizing strong optomechanical dispersive or dissipative type coupling, which provides a platform to explore the new regimes of optomechanical interaction. The addition of different strong coupling and mechanical (nuclear) anharmonicities to the optical cavity establishes a modified splitting dynamics in the absorption spectrum and shows that the ground-state bleach of coupled W(CO)6-cavity has a broad, multisigned spectral response. This work demonstrates the possibility of systematic and predictive modification of the multimode spectroscopy of optomechanical W(CO)6-cavity polariton system.

Fermi-phase-induced interference in the reaction between Cl and vibrationally excited CH3D.

Mode selectivity is a well-established concept in chemical dynamics. A polyatomic molecule possesses multiple vibrational modes and the mechanical couplings between them can result in complicated anharmonic motions that defy a simple oscillatory description. A prototypical example of this is Fermi-coupled vibration, in which an energy-split eigenstate executes coherent nuclear motion that is comprised of the constituent normal modes with distinctive phases. Will this vibrational phase affect chemical reactivity? How can this phase effect be disentangled from more classical amplitude effects? Here, to address these questions, we study the reaction of Cl with a pair of Fermi states of CH3D(v1-I and v1-II). We find that the reactivity ratio of (v1-I)/(v1-II) in forming the CH2D(v = 0) + HCl(v) products deviates significantly from that permitted by the conventional reactivity-borrowing framework. Based on a proposed metric, this discrepancy can only be explained when the scattering interferences mediated by the CH3D vibrational phases are explicitly considered, which expands the concept of vibrational control of chemical reactivity into the quantum regime.

Structural speciation in chemical reactivity profiling of binary-ternary systems of Ni(II) with iminodialcohol and aromatic chelators

The importance of structural speciation in the control of chemical reactivity in Ni(II) binary-ternary systems, involving (O,O,N)-containing substrates (1,1′-iminodi-2-propanol), and aromatic chelators (2,2′-bipyridine, 1,10-phenanthroline), prompted the systematic synthesis of new crystalline materials characterized by elemental analysis, FT-IR, UV-Visible, Luminescence, magnetic susceptibility, and X-ray crystallography. The structures contain mononuclear octahedral assemblies, the lattice architecture of which exemplifies reaction conditions under which conformational variants and solvent-associated lattice-imposed complexes are assembled. Transformations between complex species denote their association with reactivity pathways, suggesting alternate synthetic methodologies for their isolation. Theoretical work (Hirshfeld, Electrostatic Potential, DFT) signifies the impact of crystal structure on energy profiles of the generated species. The arisen physicochemical profiles of all compounds portray a well-configured interwoven network of pathways, projecting strong connection between structural speciation and Ni(II) reactivity patterns in organic-solvent media. The collective results provide well-defined parameterized profiles, poised to influence the synthesis of new Ni(II)-iminodialcohol materials with specified structural-magneto-optical properties.

A comparison of strategies for state‐selective coherent Raman excitation

AbstractWe report on the theoretical and experimental evaluation of state‐selective bond activation for coherent Raman spectroscopy and control of chemical reactivity. We compare six different strategies for state‐selective activation using shaped broadband femtosecond laser pulses. Results for a pair of long pulses with different wavelengths are also considered. For each of these approaches, we report on their theoretical and experimental ability to excite a desired vibrational mode while minimizing excitation of other modes including harmonics. We find that the double parabola spectral phase function gives the most intense Raman excitation with 10 cm−1 selectivity with the lowest background. The sinusoidal phase function produces intense Raman excitation with high selectivity but gives a series of harmonic excitations which could hinder selectivity. Implications of this study on several fields ranging from sensing, to controlling chemical reactions, and selective excited state excitation by X‐ray pulses are discussed.

Control of nuclear dynamics in the benzene cation by electronic wavepacket composition

The study of coupled electron-nuclear dynamics driven by coherent superpositions of electronic states is now possible in attosecond science experiments. The objective is to understand the electronic control of chemical reactivity. In this work we report coherent 8-state non-adiabatic electron-nuclear dynamics simulations of the benzene radical cation. The computations were inspired by the extreme ultraviolet (XUV) experimental results in which all 8 electronic states were prepared with significant population. Our objective was to study the nuclear dynamics using various bespoke coherent electronic state superpositions as initial conditions in the Quantum-Ehrenfest method. The original XUV measurements were supported by Multi-configuration time-dependent Hartree (MCTDH) simulations, which suggested a model of successive passage through conical intersections. The present computations support a complementary model where non-adiabatic events are seen far from a conical intersection and are controlled by electron dynamics involving non-adjacent adiabatic states. It proves to be possible to identify two superpositions that can be linked with two possible fragmentation paths.

Stereoelectronic power of oxygen in control of chemical reactivity: the anomeric effect is not alone.

Although carbon is the central element of organic chemistry, oxygen is the central element of stereoelectronic control in organic chemistry. Generally, a molecule with a C-O bond has both a strong donor (a lone pair) and a strong acceptor (e.g., a σ*C-O orbital), a combination that provides opportunities to influence chemical transformations at both ends of the electron demand spectrum. Oxygen is a stereoelectronic chameleon that adapts to the varying situations in radical, cationic, anionic, and metal-mediated transformations. Arguably, the most historically important stereoelectronic effect is the anomeric effect (AE), i.e., the axial preference of acceptor groups at the anomeric position of sugars. Although AE is generally attributed to hyperconjugative interactions of σ-acceptors with a lone pair at oxygen (negative hyperconjugation), recent literature reports suggested alternative explanations. In this context, it is timely to evaluate the fundamental connections between the AE and a broad variety of O-functional groups. Such connections illustrate the general role of hyperconjugation with oxygen lone pairs in reactivity. Lessons from the AE can be used as the conceptual framework for organizing disjointed observations into a logical body of knowledge. In contrast, neglect of hyperconjugation can be deeply misleading as it removes the stereoelectronic cornerstone on which, as we show in this review, the chemistry of organic oxygen functionalities is largely based. As negative hyperconjugation releases the "underutilized" stereoelectronic power of unshared electrons (the lone pairs) for the stabilization of a developing positive charge, the role of orbital interactions increases when the electronic demand is high and molecules distort from their equilibrium geometries. From this perspective, hyperconjugative anomeric interactions play a unique role in guiding reaction design. In this manuscript, we discuss the reactivity of organic O-functionalities, outline variations in the possible hyperconjugative patterns, and showcase the vast implications of AE for the structure and reactivity. On our journey through a variety of O-containing organic functional groups, from textbook to exotic, we will illustrate how this knowledge can predict chemical reactivity and unlock new useful synthetic transformations.

Recent Progress in the Manipulation of Molecules with DC Electric Fields.

The structure and reactivity of a molecule in the condensed phase are governed by its intermolecular interactions with the surrounding environment. The multipole expansion of each molecule in the condensed phase indicates that the intermolecular interactions are essentially electrostatic (e.g., ion-dipole, dipole-dipole, dipole-quadrupole, dipole-induced dipole). The electrostatic field is a fundamental language of intermolecular communications. Therefore, understanding the influence of the electrostatic field on a molecule, that is, the mechanisms by which an electrostatic field manipulates a molecule, from the perspective of molecular structure, energy states, and dynamics is indispensable for illustrating and, by extension, controlling the chemistry in molecular systems.In this Account, we describe the recent progress made in manipulation of molecular processes using an external DC electrostatic field. An electrostatic field with unprecedentedly high strength (≤4 × 108 V/m) was applied in a controlled manner across a molecular film sample using the ice film nanocapacitor method. This field strength is comparable in magnitude to that of weak intermolecular interactions such as van der Waals interactions in the condensed phases. The samples were prepared using a thin film growing technique in vacuum to obtain the desired chemically tailored molecular systems. The examples of prepared systems included small molecules and molecular clusters isolated in cryogenic Ar matrices, frozen molecular films in amorphous or crystalline phase, and interfaces of multilayered molecular films. The response of the molecules to the external field was monitored by reflection-absorption infrared spectroscopy. This approach allowed us to investigate a variety of molecular systems with various intermolecular strength and environments under the influence of strong electrostatic fields. The range of observed molecular behaviors includes the manipulation of molecular orientation, intramolecular dynamics, and proton transfer reactions as an example of stereodynamic control of chemical reactivity. These observations improve our understanding of molecular behaviors in strong electric fields and broaden our perspective on electrostatic manipulation of molecules. This information is also relevant to a variety of research topics in physical and biological sciences where electric fields play a role in molecular and biological functions.

Chemical Activation of Water Molecule by Collision with Spin–Orbit-State-Selected Vanadium Cation: Quantum-Electronic-State Control of Chemical Reactivity

We have obtained absolute integral cross sections (σ's) for the reactions of spin-orbit-state-selected vanadium cations, V+[a5DJ(J = 0, 2), a5FJ(J = 1, 2), and a3FJ(J = 2, 3)], with a water molecule (H2O) in the center-of-mass collision energy range Ecm = 0.1-10.0 eV. On the basis of these state-selected σ curves (σ versus Ecm plots) observed, three reaction product channels, VO+ + H2, VH+ + OH, and VOH+ + H, from the V+ + H2O reaction are unambiguously identified. Contrary to the previous guided ion beam study of the V+(a5DJ) + D2O reaction, we have observed the formation of the VO+ + H2 channel from the V+(a5DJ) + H2O ground reactant state at low Ecm's (<3.0 eV). No spin-orbit J-state dependences for the σ curves of individual electronic states are discernible, indicating that spin-orbit interactions are weak with little effect on chemical reactivity of the titled reaction. For the three product channels identified, the triplet σ(a3FJ) values are overwhelmingly higher than the quintet σ(a5DJ) and σ(a5FJ) values, showing that the reaction is governed by a "weak quintet-triplet spin crossing" mechanism, favoring the conservation of total electron spins. The σ curves for exothermic product channels are found to exhibit a rapid decreasing profile as Ecm is increased, an observation consistent with the prediction of the charge-dipole and induced-dipole orbiting model. This experiment shows that the V+ + H2O reaction can be controlled effectively to produce predominantly the VO+ + H2 channel via the V+(a3FJ) + H2O reaction at low Ecm's (≤0.1 eV) and that the ion-molecule reaction dynamics can be altered readily by selecting the electronic state of V+ cation. On the basis of the measured Ecm thresholds for the σ(a5DJ, a5FJ, and a3FJ: VH+) and σ(a5DJ, a5FJ, and a3FJ: VOH+) curves, we have deduced upper bound values of 2.6 ± 0.2 and 4.3 ± 0.3 eV for the 0 K bond dissociation energies, D0(V+-H) and D0(V+-OH), respectively. After correcting for the kinetic energy distribution resulting from the Doppler broadening effect of the H2O molecule, we obtain D0(V+-H) = 2.2 ± 0.2 eV and D0(V+-OH) = 4.0 ± 0.3 eV, which are in agreement with D0 determinations obtained by σ curve simulations.

Photomodulated Spatially Confined Chemical Reactivity in a Single Silver Nanoprism

Single-atom and single-particle catalysis is an area of considerable topical interest due to their potential in explaining important fundamental processes and applications across several areas. An interesting avenue in single-particle catalysis is spatial control of chemical reactivity within the particle by employing light as an external stimulus. To demonstrate this concept, we report galvanic replacement reactions (GRRs) as a spatial marker of subparticle chemical reactivity of a silver nanoprism with AuCl4- ions under optical excitation. The location of a GRR within a single Ag nanoprism can be spatially controlled depending on the plasmon mode excited. This leads to chemomorphological transformation of Ag nanoprisms into interesting Ag-Au structures. This spatial biasing effect is attributed to localized hot electron injection from the tips and edges of the silver nanoprisms to the adjacent reactants that correlate with excitation of different surface plasmon modes. The study also employs low-energy-loss EELS mapping to additionally probe the spatially confined redox reaction within a silver nanoprism. The findings presented here allow the visualization of a plasmon-driven subparticle chemical transformation with high resolution. The selective optical excitation of surface plasmon eigenmodes of anisotropic nanoparticles offers opportunities to spatially modulate chemical transformations mediated by hot electron transfer.

Data enhanced Hammett-equation: reaction barriers in chemical space.

It is intriguing how the Hammett equation enables control of chemical reactivity throughout chemical space by separating the effect of substituents from chemical process variables, such as reaction mechanism, solvent, or temperature. We generalize Hammett's original approach to predict potential energies of activation in non aromatic molecular scaffolds with multiple substituents. We use global regression to optimize Hammett parameters ρ and σ in two experimental datasets (rate constants for benzylbromides reacting with thiols and ammonium salt decomposition), as well as in a synthetic dataset consisting of computational activation energies of ∼2400 SN2 reactions, with various nucleophiles and leaving groups (–H, –F, –Cl, –Br) and functional groups (–H, –NO2, –CN, –NH3, –CH3). Individual substituents contribute additively to molecular σ with a unique regression term, which quantifies the inductive effect. The position dependence of substituents can be modeled by a distance decaying factor for SN2. Use of the Hammett equation as a base-line model for Δ-machine learning models of the activation energy in chemical space results in substantially improved learning curves reaching low prediction errors for small training sets.

Solid wetting-layers in inorganic nano-reactors: the water in imogolite nanotube case.

By combined use of wide-angle X-ray scattering, thermo-gravimetric analysis, inelastic neutron scattering, density functional theory and density functional theory molecular dynamics simulations, we investigate the structure, dynamics and stability of the water wetting-layer in single-walled aluminogermanate imogolite nanotubes (SW Ge-INTs): an archetypal system for synthetically controllable and monodisperse nano-reactors. We demonstrate that the water wetting-layer is strongly bound and solid-like up to 300 K under atmospheric pressure, with dynamics markedly different from that of bulk water. Atomic-scale characterisation of the wetting-layer reveals organisation of the H2O molecules in a curved triangular sublattice stabilised by the formation of three H-bonds to the nanotube's inner surface, with covalent interactions sufficiently strong to promote energetically favourable decoupling of the H2O molecules in the adlayer. The evidenced changes in the local composition, structure, electrostatics and dynamics of the Ge-INT's inner surface upon the formation of the solid wetting-layer demonstrate solvent-mediated functionalisation of the nanotube's cavity at room temperature and pressure, suggesting new strategies for the design of nano-rectors towards potential control of chemical reactivity in nano-confined volumes.

The core design of a Small Modular Pressurised Water Reactor for commercial marine propulsion

If international agreements regarding the need to significantly reduce greenhouse gas emissions are to be met then there is a high probability that the shipping industry will have to dramatically reduce its greenhouse gas emissions. For emission reductions from ships greater than around 40% then alternatives to fossil fuels - such as nuclear energy - will very likely be required. A Small Modular Pressurised Water Reactor design has been developed specifically to meet the requirements of a large container ship with a power requirement of 110 MWe. Container ships have a number of requirements - including a small crew size and reduced outages associated with refuelling - that result in a greater focus on design simplifications, including the elimination of the chemical reactivity control system during power operation and a long core life.We have developed a novel, soluble-boron free, low power density core that does not require refuelling for 15 years. The neutronic and fuel performance behaviour of this system has been studied with conventional UO2 fuel. The size of the pressure vessel has been limited to 3.5 m in diameter. Furthermore, to ensure the survivability of the cladding material, the coolant outlet temperature has been reduced to 285 °C from 320 °C as in conventional GWe-class PWRs, with a resulting reduction in thermal efficiency to 25%. The UO2 core design was able to satisfactorily meet the majority of requirements placed upon the system assuming that fuel rod burnups can be limited to 100 GWd/tHM. The core developed here represents the first workable design of a commercial marine reactor using conventional fuel, which makes realistic the idea of using nuclear reactors for shipping.

Boron nitride nanoresonators for phonon-enhanced molecular vibrational spectroscopy at the strong coupling limit

Enhanced light-matter interactions are the basis of surface-enhanced infrared absorption (SEIRA) spectroscopy, and conventionally rely on plasmonic materials and their capability to focus light to nanoscale spot sizes. Phonon polariton nanoresonators made of polar crystals could represent an interesting alternative, since they exhibit large quality factors, which go far beyond those of their plasmonic counterparts. The recent emergence of van der Waals crystals enables the fabrication of high-quality nanophotonic resonators based on phonon polaritons, as reported for the prototypical infrared-phononic material hexagonal boron nitride (h-BN). In this work we use, for the first time, phonon-polariton-resonant h-BN ribbons for SEIRA spectroscopy of small amounts of organic molecules in Fourier transform infrared spectroscopy. Strikingly, the interaction between phonon polaritons and molecular vibrations reaches experimentally the onset of the strong coupling regime, while numerical simulations predict that vibrational strong coupling can be fully achieved. Phonon polariton nanoresonators thus could become a viable platform for sensing, local control of chemical reactivity and infrared quantum cavity optics experiments.

ChemInform Abstract: Control of Chemical Reactivity by Transition‐State and Beyond

AbstractReview: 138 refs.

Control of chemical reactivity by transition-state and beyond.

It has been long established that the transition state for an activated reaction controls the overall reactivity, serving as the bottleneck for reaction flux. However, the role of the transition state in regulating quantum state resolved reactivity has only been addressed more recently, thanks to advances in both experimental and theoretical techniques. In this perspective, we discuss some recent advances in understanding mode-specific reaction dynamics in bimolecular reactions, mainly focusing on the X + H2O/CH4 (X = H, F, Cl, and O(3P)) systems, extensively studied in our groups. These advances shed valuable light on the importance of the transition state in mode-specific and steric dynamics of these prototypical reactions. It is shown that many mode-specific phenomena can be understood in terms of a transition-state based model, which assumes in the sudden limit that the ability of a reactant mode for promoting the reaction stems from its coupling with the reaction coordinate at the transition state. Yet, in some cases the long-range anisotropic interactions in the entrance (or exit) valley, which govern how the trajectories reach (or leave) the transition state, also come into play, thus modifying the reactive outcomes.

Perspective: Vibrational-induced steric effects in bimolecular reactions.

The concept of preferred collision geometry in a bimolecular reaction is at the heart of reaction dynamics. Exemplified by a series of crossed molecular beam studies on the reactions of a C-H stretch-excited CHD3(v1 = 1) with F, Cl, and O((3)P) atoms, two types of steric control of chemical reactivity will be highlighted. A passive control is governed in a reaction with strong anisotropic entry valley that can significantly steer the incoming trajectories. This disorientation effect is illustrated by the F and O((3)P) + CHD3(v1 = 1) reactions. In the former case, the long-range anisotropic interaction acts like an optical "negative" lens by deflecting the trajectories away from the favored transition-state geometry, and thus inhibiting the bond rupture of the stretch-excited CHD3. On the contrary, the interaction between O((3)P) and CHD3(v1 = 1) behaves as a "positive" lens by funneling the large impact-parameter collisions into the cone of acceptance, and thereby enhances the reactivity. As for reactions with relatively weak anisotropic interactions in the entry valley, an active control can be performed by exploiting the polarization property of the infrared excitation laser to polarize the reactants in space, as demonstrated in the reaction of Cl with a pre-aligned CHD3(v1 = 1) reactant. A simpler case, the end-on versus side-on collisions, will be elucidated for demonstrating a means to disentangle the impact-parameter averaging. A few general remarks about some closely related issues, such as mode-, bond-selectivity, and Polanyi's rules, are made.

Dicopper(II) metallacyclophanes as multifunctional magnetic devices: a joint experimental and computational study.

Metallosupramolecular complexes constitute an important advance in the emerging fields of molecular spintronics and quantum computation and a useful platform in the development of active components of spintronic circuits and quantum computers for applications in information processing and storage. The external control of chemical reactivity (electro- and photochemical) and physical properties (electronic and magnetic) in metallosupramolecular complexes is a current challenge in supramolecular coordination chemistry, which lies at the interface of several other supramolecular disciplines, including electro-, photo-, and magnetochemistry. The specific control of current flow or spin delocalization through a molecular assembly in response to one or many input signals leads to the concept of developing a molecule-based spintronics that can be viewed as a potential alternative to the classical molecule-based electronics. A great variety of factors can influence over these electronically or magnetically coupled, metallosupramolecular complexes in a reversible manner, electronic or photonic external stimuli being the most promising ones. The response ability of the metal centers and/or the organic bridging ligands to the application of an electric field or light irradiation, together with the geometrical features that allow the precise positioning in space of substituent groups, make these metal-organic systems particularly suitable to build highly integrated molecular spintronic circuits. In this Account, we describe the chemistry and physics of dinuclear copper(II) metallacyclophanes with oxamato-containing dinucleating ligands featuring redox- and photoactive aromatic spacers. Our recent works on dicopper(II) metallacyclophanes and earlier ones on related organic cyclophanes are now compared in a critical manner. Special focus is placed on the ligand design as well as in the combination of experimental and computational methods to demonstrate the multifunctionality nature of these metallosupramolecular complexes. This new class of oxamato-based dicopper(II) metallacyclophanes affords an excellent synthetic and theoretical set of models for both chemical and physical fundamental studies on redox- and photo-triggered, long-distance electron exchange phenomena, which are two major topics in molecular magnetism and molecular electronics. Apart from their use as ground tests for the fundamental research on the relative importance of the spin delocalization and spin polarization mechanisms of the electron exchange interaction through extended π-conjugated aromatic ligands in polymetallic complexes, oxamato-based dicopper(II) metallacyclophanes possessing spin-containing electro- and chromophores at the metal and/or the ligand counterparts emerge as potentially active (magnetic and electronic) molecular components to build a metal-based spintronic circuit. They are thus unique examples of multifunctional magnetic complexes to get single-molecule spintronic devices by controlling and allowing the spin communication, when serving as molecular magnetic couplers and wires, or by exhibiting bistable spin behavior, when acting as molecular magnetic rectifiers and switches. Oxamato-based dicopper(II) metallacyclophanes also emerge as potential candidates for the study of coherent electron transport through single molecules, both experimentally and theoretically. The results presented herein, which are a first step in the metallosupramolecular approach to molecular spintronics, intend to attract the attention of physicists and materials scientists with a large expertice in the manipulation and measurement of single-molecule electron transport properties, as well as in the processing and addressing of molecules on different supports.

Toward control of electron transfer in donor-acceptor molecules by bond-specific infrared excitation.

Electron transfer (ET) from donor to acceptor is often mediated by nuclear-electronic (vibronic) interactions in molecular bridges. Using an ultrafast electronic-vibrational-vibrational pulse-sequence, we demonstrate how the outcome of light-induced ET can be radically altered by mode-specific infrared (IR) excitation of vibrations that are coupled to the ET pathway. Picosecond narrow-band IR excitation of high-frequency bridge vibrations in an electronically excited covalent trans-acetylide platinum(II) donor-bridge-acceptor system in solution alters both the dynamics and the yields of competing ET pathways, completely switching a charge separation pathway off. These results offer a step toward quantum control of chemical reactivity by IR excitation.