Direct and Indirect Pathways of CdTeSe Magic-Size Cluster Isomerization Induced by Surface Ligands at Room Temperature

Yusha Yang; Qiu Shen; Chunchun Zhang; Nelson Rowell; Meng Zhang; Xiaoqin Chen; Chaoran Luan; Kui Yu

doi:10.1021/acscentsci.2c01394

Direct and Indirect Pathways of CdTeSe Magic-Size Cluster Isomerization Induced by Surface Ligands at Room Temperature

ACS Cent Sci. 2023 Mar 8;9(3):519-530. doi: 10.1021/acscentsci.2c01394. eCollection 2023 Mar 22.

Authors

Yusha Yang¹, Qiu Shen¹, Chunchun Zhang², Nelson Rowell³, Meng Zhang⁴, Xiaoqin Chen¹, Chaoran Luan⁵, Kui Yu^{1

4}

Affiliations

¹ Engineering Research Center in Biomaterials, Sichuan University, Chengdu, Sichuan 610065, P. R. China.
² Analytical & Testing Center, Sichuan University, Chengdu, Sichuan 610065, P. R. China.
³ Metrology Research Centre, National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada.
⁴ Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, Sichuan 610065, P. R. China.
⁵ Laboratory of Ethnopharmacology, West China School of Medicine, West China Hospital, Sichuan University, Chengdu, Sichuan 610065, P. R. China.

Abstract

The field of isomerization reactions for colloidal semiconductor magic-size clusters (MSCs) remains largely unexplored. Here, we show that MSCs isomerize via two fundamental pathways that are regulated by the acidity and amount of an incoming ligand, with CdTeSe as the model system. When MSC-399 isomerizes to MSC-422 at room temperature, the peak red-shift from 399 to 422 nm is continuous (pathway 1) and/or stepwise (pathway 2) as monitored in situ and in real time by optical absorption spectroscopy. We propose that pathway 1 is direct, with intracluster configuration changes and a relatively large energy barrier. Pathway 2 is indirect, assisted by the MSC precursor compounds (PCs), from MSC-399 to PC-399 to PC-422 to MSC-422. Pathway 1 is activated when PC-422 to MSC-422 is suppressed. Our findings unambiguously suggest that when a change occurs directly on a nanospecies, its absorption peak continuously shifts. The present study provides an in-depth understanding of the transformative behavior of MSCs via ligand-induced isomerization upon external chemical stimuli.