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

Shahnawaz Rafiq; Máté J. Bezdek; Paul J. Chirik; Gregory D. Scholes

doi:10.1016/j.chempr.2018.11.003

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

Shahnawaz Rafiq, Máté J. Bezdek, Paul J. Chirik, Gregory D. Scholes

Chemistry

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

The traditional view of a chemical change is inherently local and classical, and such a change relies on a mix of thermodynamic and kinetic parameters to control reactivity. Often, the thermodynamic stability of chemical bonds necessitates significant energy input for activation. One fundamental question is potentially transformative: can quantum mechanics enable selective bond activation? A possible approach involves strategic input of energy to reaction-specific vibrational levels. Toward this goal, our work describes the coupling of vibrational motions in a terpyridine-molybdenum complex hosting a nonreactive substrate—dinitrogen. Ultrafast coherence spectroscopies revealed a Fermi-resonance coupling mechanism connecting in-plane breathing motion of the light-harvesting terpyridines with the stretching motion of the spatially disparate dinitrogen bridge. Notably, the coupling is significantly enhanced in the photoexcited state. This Fermi resonance indicates an energy conduit that drives the two motions in sync and thereby amplifies vibrational energy exchange. Achieving selective bond activation by bridging vibrations could present a quantum-inspired design principle in synthetic chemistry.

Original language	English
Pages (from-to)	402-416
Number of pages	15
Journal	Chem
Volume	5
Issue number	2
DOIs	https://doi.org/10.1016/j.chempr.2018.11.003
State	Published - Feb 14 2019

Bibliographical note

Funding Information:
S.R. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy Basic Energy Sciences program through grant no. DE-SC0015429 . G.D.S. also acknowledges support from the W.M. Keck Foundation through award no. 1005586. M.J.B. and P.J.C. acknowledge support from the Basic Energy Sciences program of the US Department of Energy Office of Science ( DE-SC0006498 ). M.J.B. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship (PGS-D) as well as Princeton University for an Edward C. Taylor Fellowship. S.R. thanks the Imaging and Analysis Center in PRISM at Princeton University for providing access to the Raman facility.

Funding Information:
S.R. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy Basic Energy Sciences program through grant no. DE-SC0015429. G.D.S. also acknowledges support from the W.M. Keck Foundation through award no. 1005586. M.J.B. and P.J.C. acknowledge support from the Basic Energy Sciences program of the US Department of Energy Office of Science (DE-SC0006498). M.J.B. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship (PGS-D) as well as Princeton University for an Edward C. Taylor Fellowship. S.R. thanks the Imaging and Analysis Center in PRISM at Princeton University for providing access to the Raman facility.

Publisher Copyright:
© 2018 Elsevier Inc.

Keywords

Fermi resonance
SDG7: Affordable and clean energy
bond activation
coherence spectroscopy
high-frequency modes
molybdenum terpyridine complex
photoactivation
quantum coherences
quantum energy flow
vibrational coupling
vibronic enhancement
wavepackets

ASJC Scopus subject areas

Chemistry (all)
Biochemistry
Environmental Chemistry
Chemical Engineering (all)
Biochemistry, medical
Materials Chemistry

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10.1016/j.chempr.2018.11.003

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title = "Dinitrogen Coupling to a Terpyridine-Molybdenum Chromophore Is Switched on by Fermi Resonance",

abstract = "The traditional view of a chemical change is inherently local and classical, and such a change relies on a mix of thermodynamic and kinetic parameters to control reactivity. Often, the thermodynamic stability of chemical bonds necessitates significant energy input for activation. One fundamental question is potentially transformative: can quantum mechanics enable selective bond activation? A possible approach involves strategic input of energy to reaction-specific vibrational levels. Toward this goal, our work describes the coupling of vibrational motions in a terpyridine-molybdenum complex hosting a nonreactive substrate—dinitrogen. Ultrafast coherence spectroscopies revealed a Fermi-resonance coupling mechanism connecting in-plane breathing motion of the light-harvesting terpyridines with the stretching motion of the spatially disparate dinitrogen bridge. Notably, the coupling is significantly enhanced in the photoexcited state. This Fermi resonance indicates an energy conduit that drives the two motions in sync and thereby amplifies vibrational energy exchange. Achieving selective bond activation by bridging vibrations could present a quantum-inspired design principle in synthetic chemistry.",

keywords = "Fermi resonance, SDG7: Affordable and clean energy, bond activation, coherence spectroscopy, high-frequency modes, molybdenum terpyridine complex, photoactivation, quantum coherences, quantum energy flow, vibrational coupling, vibronic enhancement, wavepackets",

author = "Shahnawaz Rafiq and Bezdek, {M{\'a}t{\'e} J.} and Chirik, {Paul J.} and Scholes, {Gregory D.}",

note = "Funding Information: S.R. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy Basic Energy Sciences program through grant no. DE-SC0015429 . G.D.S. also acknowledges support from the W.M. Keck Foundation through award no. 1005586. M.J.B. and P.J.C. acknowledge support from the Basic Energy Sciences program of the US Department of Energy Office of Science ( DE-SC0006498 ). M.J.B. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship (PGS-D) as well as Princeton University for an Edward C. Taylor Fellowship. S.R. thanks the Imaging and Analysis Center in PRISM at Princeton University for providing access to the Raman facility. Funding Information: S.R. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy Basic Energy Sciences program through grant no. DE-SC0015429. G.D.S. also acknowledges support from the W.M. Keck Foundation through award no. 1005586. M.J.B. and P.J.C. acknowledge support from the Basic Energy Sciences program of the US Department of Energy Office of Science (DE-SC0006498). M.J.B. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship (PGS-D) as well as Princeton University for an Edward C. Taylor Fellowship. S.R. thanks the Imaging and Analysis Center in PRISM at Princeton University for providing access to the Raman facility. Publisher Copyright: {\textcopyright} 2018 Elsevier Inc.",

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AU - Scholes, Gregory D.

N1 - Funding Information: S.R. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy Basic Energy Sciences program through grant no. DE-SC0015429 . G.D.S. also acknowledges support from the W.M. Keck Foundation through award no. 1005586. M.J.B. and P.J.C. acknowledge support from the Basic Energy Sciences program of the US Department of Energy Office of Science ( DE-SC0006498 ). M.J.B. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship (PGS-D) as well as Princeton University for an Edward C. Taylor Fellowship. S.R. thanks the Imaging and Analysis Center in PRISM at Princeton University for providing access to the Raman facility. Funding Information: S.R. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences, and Biosciences of the US Department of Energy Basic Energy Sciences program through grant no. DE-SC0015429. G.D.S. also acknowledges support from the W.M. Keck Foundation through award no. 1005586. M.J.B. and P.J.C. acknowledge support from the Basic Energy Sciences program of the US Department of Energy Office of Science (DE-SC0006498). M.J.B. thanks the Natural Sciences and Engineering Research Council of Canada for a predoctoral fellowship (PGS-D) as well as Princeton University for an Edward C. Taylor Fellowship. S.R. thanks the Imaging and Analysis Center in PRISM at Princeton University for providing access to the Raman facility. Publisher Copyright: © 2018 Elsevier Inc.

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N2 - The traditional view of a chemical change is inherently local and classical, and such a change relies on a mix of thermodynamic and kinetic parameters to control reactivity. Often, the thermodynamic stability of chemical bonds necessitates significant energy input for activation. One fundamental question is potentially transformative: can quantum mechanics enable selective bond activation? A possible approach involves strategic input of energy to reaction-specific vibrational levels. Toward this goal, our work describes the coupling of vibrational motions in a terpyridine-molybdenum complex hosting a nonreactive substrate—dinitrogen. Ultrafast coherence spectroscopies revealed a Fermi-resonance coupling mechanism connecting in-plane breathing motion of the light-harvesting terpyridines with the stretching motion of the spatially disparate dinitrogen bridge. Notably, the coupling is significantly enhanced in the photoexcited state. This Fermi resonance indicates an energy conduit that drives the two motions in sync and thereby amplifies vibrational energy exchange. Achieving selective bond activation by bridging vibrations could present a quantum-inspired design principle in synthetic chemistry.

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

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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