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

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

Research output: Contribution to journalArticlepeer-review

13 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 languageEnglish (US)
Pages (from-to)402-416
Number of pages15
JournalChem
Volume5
Issue number2
DOIs
StatePublished - Feb 14 2019

All Science Journal Classification (ASJC) codes

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

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