Dinitrogen Coupling to a Terpyridine-Molybdenum Chromophore Is Switched on by Fermi Resonance

Abstract

The grand challenge of selectively depositing energy into the reaction-specific motions of molecules motivates quantum-inspired strategies for bond activation. Toward this goal, the coherence spectroscopic study of a dinitrogen-bridged molybdenum complex revealed Fermi-resonance coupling between the lightharvesting terpyridine-molybdenum chromophore and dinitrogen-a potential reaction site. This coupling results in quantum mechanical mixing of two spatially disparate high-frequency vibrations and is proposed to open quantum energy flow pathways into reaction-specific motions, thereby giving rise to selective bond activation by vibrational linking.

Tuning Molecular Vibrational Energy Flow within an Aromatic Scaffold via Anharmonic Coupling

“…This work and previous literature show that the rate of energy transfer can be tuned by the strength of the Fermi resonance. [44][45] Also, the IVR studied here is relevant in the design of energy diodes. 30,39 In particular, our studies demonstrate that vibrational energy rectification can be exploited for molecular electronics.…”

“…However, Zheng and coworkers have developed methods to design molecules that decouple the modes making intermolecular vibrational energy transfer the preferred route. 22,43 VER plays a vital role in many physical and chemical processes, such as chemical reactions where selected vibrational energy flow influences the reaction coordinate aiding in synthetic chemistry, 20,22,40,[43][44][45][46] molecular electronics and electrochemistry, [38][39][47][48][49] measuring three dimensional structures of molecular systems, 24,[50][51][52][53] and energetic properties of transition metals. 20-21, 41, 48 VER also influences protein functions through hydrogen bonding along protein backbones, 32,54 formation of secondary and tertiary structures, 34 and allosteric communication.…”

Report of the Basic Energy Sciences Roundtable on Liquid Solar Fuels

“…New research is needed to identify unique proton-coupled electron transfer reactivity from electronic excited states that will enable fuel-forming reactions to be driven from single-component absorber-catalysts that can access reaction trajectories unavailable to thermal catalysts. Separately, bond-localized energy capture has recently been observed, suggesting that energy-transfer processes that funnel excitation to selective bonds can, in principle, provide mechanisms for liquid fuels catalysis not accessible by thermal catalysis 136 . Research is needed to determine if bond activation can be promoted from these vibronically excited states.…”

Rhodapentalenes: Pincer Complexes with Internal Aromaticity

“…Since the first reports in the late 1970s (Kelly et al., 1971, Moulton and Shaw, 1976, van Koten et al., 1978), pincer complexes have made great progresses and have been widely used in the fields of synthesis (Martinez et al., 2016, Pell et al., 2017, Rafiq et al., 2019), catalysis (Gao et al., 2018, Luque-Urrutia et al., 2019, Nielsen et al., 2013, Niu et al., 2019, Zhang et al., 2018), materials science (Albrecht et al., 2000, To et al., 2017, Zhang et al., 2017a), and biological systems (Desguin et al., 2015, Fellner et al., 2017). This has had an effect on the development of inorganic chemistry, materials chemistry, supramolecular chemistry, and bioorganometallics chemistry and on bond-making and bond-breaking processes (Albrecht and Lindner, 2011, Albrecht and van Koten, 2001, Gunanathan and Milstein, 2014, Kumar et al., 2017, Leis et al., 2008, Li et al., 2019, Morales-Morales, 2018, O’Reilly and Veige, 2014, Szabó and Wendt, 2014).…”