Spatial and temporal control over photoresponsive nanoclusters
Ying Xu, Mengfan Chang, Hao Li, Ning Zhang, Siqi Li, Pu Wang, Yong Pei, Xi Kang, Manzhou Zhu
Abstract
ABSTRACT Although cluster species undergo efficient photoresponsive transformations in dilute solutions, their solid-state materials suffer from severely impeded responsiveness due to insufficient motional freedom. Here, we present a photochemical approach that enables spatial and temporal control over nanocluster structure/size conversions in the crystalline state. The Cu18 nanocluster, whether in solution or in solid form, undergoes a photoinduced transformation when exposed to 365-nm light, resulting in a size-reduced Cu14 nanocluster. The single-atom alloy counterpart, Ag1Cu17, possesses a remarkably enhanced efficiency towards the photoinduced conversion to form the same cluster product. The comparable photoinduced conversion efficiencies between Cu18 and Ag1Cu17 are monitored by using time-dependent characterizations and further rationalized by using theoretical calculations. The high photoconversion efficiency of crystalline nanocluster materials allows the precise spatial and temporal control of solid-state transformations at the micrometer scale by using femtosecond cold laser technology or by controlling the irradiation time of ultraviolet light. This study introduces a novel pair of clusters with comparable photoinduced conversion characteristics, allowing atomic-level characterizations and an in-depth understanding of the photochemical behavior of metal nanoclusters. Furthermore, the findings in this work are expected to facilitate the design of cluster-based solid-state nanomaterials for downstream photoresponsive applications.