Spin–vibronic coherence drives singlet–triplet conversion

Shahnawaz Rafiq, Nicholas P. Weingartz, Sarah Kromer, Felix N. Castellano, Lin X. Chen

Research output: Contribution to journalArticlepeer-review

13 Scopus citations

Abstract

Design-specific control over the transitions between excited electronic states with different spin multiplicities is of the utmost importance in molecular and materials chemistry1–3. Previous studies have indicated that the combination of spin–orbit and vibronic effects, collectively termed the spin–vibronic effect, can accelerate quantum-mechanically forbidden transitions at non-adiabatic crossings4,5. However, it has been difficult to identify precise experimental manifestations of the spin–vibronic mechanism. Here we present coherence spectroscopy experiments that reveal the interplay between the spin, electronic and vibrational degrees of freedom that drive efficient singlet–triplet conversion in four structurally related dinuclear Pt(II) metal–metal-to-ligand charge-transfer (MMLCT) complexes. Photoexcitation activates the formation of a Pt–Pt bond, launching a stretching vibrational wavepacket. The molecular-structure-dependent decoherence and recoherence dynamics of this wavepacket resolve the spin–vibronic mechanism. We find that vectorial motion along the Pt–Pt stretching coordinates tunes the singlet and intermediate-state energy gap irreversibly towards the conical intersection and subsequently drives formation of the lowest stable triplet state in a ratcheting fashion. This work demonstrates the viability of using vibronic coherences as probes6–9 to clarify the interplay among spin, electronic and nuclear dynamics in spin-conversion processes, and this could inspire new modular designs to tailor the properties of excited states.

Original languageEnglish
Pages (from-to)776-781
Number of pages6
JournalNature
Volume620
Issue number7975
DOIs
StatePublished - Aug 24 2023

Bibliographical note

Publisher Copyright:
© 2023, The Author(s), under exclusive licence to Springer Nature Limited.

ASJC Scopus subject areas

  • General

Fingerprint

Dive into the research topics of 'Spin–vibronic coherence drives singlet–triplet conversion'. Together they form a unique fingerprint.

Cite this