Mechanistic Origin of Favorable Substituent Effects in Excellent Cu Cyclam Based HNO Sensors

Yelu Shi, Gianna Stella, Jia Min Chu, Yong Zhang

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

HNO has broad chemical and biomedical properties. Metal complexes and derivatives are widely used to make excellent HNO sensors. However, their favorable mechanistic origins are largely unknown. Cu cyclam is a useful platform to make excellent HNO sensors including imaging agents. A quantum chemical study of Cu cyclams with various substitutions was performed, which reproduced diverse experimental reactivities. Structural, electronic, and energetic profiles along reaction pathways show the importance of HNO binding and a proton-coupled electron transfer mechanism for HNO reaction. Results reveal that steric effect is primary and electronic factor is secondary (if the redox potential is sufficient), but their interwoven effects can lead to unexpected reactivity, which looks mysterious experimentally but can be explained computationally. This work suggests rational substituent design ideas and recommends a theoretical study of a new design to save time and cost due to its subtle effect.

Original languageEnglish
Article numbere202211450
JournalAngewandte Chemie - International Edition
Volume61
Issue number45
DOIs
StatePublished - 7 Nov 2022

Keywords

  • Copper
  • Density Functional Calculations
  • Nitrogen Oxides
  • Reaction Mechanisms
  • Substituent Effects

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