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PreprintCC BYChemRxiv

Quantifying Surface-Induced Inhibition of Cu(I) Excited State Distortion Using Variable- Temperature Transient Absorption and Stern– Volmer Quenching

  • Ethan C. Lambert1,2
  • Jackson L. Nolder1,2
  • Holly O. Konrad1,2
  • Henry C. London1,2
  • Matthew C. McGarry1,2
  • J. S. Raaj Vellore Winfred1,2
  • Kenneth Hanson1,2
  1. 1Department of Chemistry & Biochemistry
  2. 2Florida State University
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Abstract

Photoexcited Cu(I) coordination complexes are known to undergo structural distortion that lowers the excited state energy, facilitates nonradiative decay, and opens the metal center to coordinative quenching of the excited state. Strategic surface binding was recently introduced as a new means of hindering excited state distortion resulting in a >10-fold increase in excited state lifetimes. Here, Stern-Volmer analysis, temperature dependent ultrafast transient absorption, and theoretical calculations reveal a near order-of-magnitude decrease in the quenching rate constant, a decrease in reorganization energies, an increased entropic penalty to accessing the transition state geometry, and a smaller change in the dihedral angle of the triplet excited state upon surface binding. Collectively, the results support that strategic surface binding is an effective strategy for inhibiting distortion of Cu(I) coordination complexes resulting in an increased excited state lifetime, decreased accessibility of coordinative quenchers, and opens the door to increasing molecular reactivity via molecule-metal oxide interfaces.

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Cite

BibTeXRIS
BibTeX
@misc{lambert2026quantifying,
  title = {{Quantifying Surface-Induced Inhibition of Cu(I) Excited State Distortion Using Variable- Temperature Transient Absorption and Stern– Volmer Quenching}},
  author = {Ethan C. Lambert and Jackson L. Nolder and Holly O. Konrad and Henry C. London and Matthew C. McGarry and J. S. Raaj Vellore Winfred and Kenneth Hanson},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008685/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008685/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Quantifying Surface-Induced Inhibition of Cu(I) Excited State Distortion Using Variable- Temperature Transient Absorption and Stern– Volmer Quenching
AU  - Ethan C. Lambert
AU  - Jackson L. Nolder
AU  - Holly O. Konrad
AU  - Henry C. London
AU  - Matthew C. McGarry
AU  - J. S. Raaj Vellore Winfred
AU  - Kenneth Hanson
PY  - 2026
DA  - 2026/09/11
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008685/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008685/v1
AB  - Photoexcited Cu(I) coordination complexes are known to undergo structural distortion that lowers the excited state energy, facilitates nonradiative decay, and opens the metal center to coordinative quenching of the excited state. Strategic surface binding was recently introduced as a new means of hindering excited state distortion resulting in a >10-fold increase in excited state lifetimes. Here, Stern-Volmer analysis, temperature dependent ultrafast transient absorption, and theoretical calculations reveal a near order-of-magnitude decrease in the quenching rate constant, a decrease in reorganization energies, an increased entropic penalty to accessing the transition state geometry, and a smaller change in the dihedral angle of the triplet excited state upon surface binding. Collectively, the results support that strategic surface binding is an effective strategy for inhibiting distortion of Cu(I) coordination complexes resulting in an increased excited state lifetime, decreased accessibility of coordinative quenchers, and opens the door to increasing molecular reactivity via molecule-metal oxide interfaces.
ER  -