Reversible Wide‐Range Tuneable Luminescence of a Dual‐Stimuli‐ Responsive Silver Cluster‐Assembled Material

Abstract

Summary of main observation and conclusion Silver cluster‐assembled materials (SCAMs) are emerging multi‐functional materials and have attracted great attention recently. In this work, we have prepared a new SCAM of {[Ag18(StBu)10(CF3COO)2(PhPO3)(PhPO3H)4(bpy‐NH2)2]∙(PhPO3H2)}n (denoted as Ag18bpy‐NH2), by a facile one‐pot method. Ag18bpy‐NH2 adopts a chain‐like structure made of Ag18 clusters bridged by bipyridyl linkers. Ag18bpy‐NH2 exhibits reversible luminescent mechanochromism upon mechanical stimulation and solvent treatment. Moreover, it also displays luminescent thermochromism with a linear relationship of the temperature to the intensity ratio of the dual emissions over a wide temperature range of 83 to 303 K. This work might provide new insights into the assembly of multifunctional stimuli‐responsive SCAMs.

Thiolate‐Protected Metal Nanoclusters: Recent Development in Synthesis, Understanding of Reaction, and Application in Energy and Environmental Field

“…[ 96,104–119 ] In addition, the regular connection of metal NCs produces new functions. [ 96,120–142 ] In the following, we discuss recent developments in alloying and regular connection.…”

“…Indeed, in recent years, there have been several reports on crystals in which metal NCs containing SR ligand were regularly linked using several means ( Table 3 ). [ 96,120–142 ]…”

One-, Two-, and Three-Dimensional Self-Assembly of Atomically Precise Metal Nanoclusters

“…Because N readily coordinates to Ag, bipyridine is often used to connect NCs containing Ag. In 2019, Zang and colleagues formed a 1D CS composed of Ag 18 (PhPO 3 )(S- t Bu) 10 (CF 3 COO) 2 (PhPO 3 H) 4 (PhPO 3 2− = phenylphosphinic diion; PhPO 3 H − = phenylphosphinic acid ion) NC nodes with bipyridine(3-amino-4,4′-bipyridine (bpy-NH 2 , Scheme 2 (4)) linkers [ 157 ]. In this experiment, NC synthesis, ligation, and crystallization were performed simultaneously in one pot ( Figure 14 A).…”

“…The inset photographs show the emission of [Ag 18 (PhPO 3 )(S- t Bu) 10 (CF 3 COO) 2 (PhPO 3 H) 4 (bpy-NH 2 ) 2 ] in the solid state under ultraviolet light irradiation at room temperature and liquid nitrogen temperature. Reproduced with permission from Reference [ 157 ]. Copyright 2019 Wiley-VCH.…”

A Silver Cluster‐Assembled Material Showing Luminescent Mechanochromism and Thermochromism

“…Ag 18 bpy‐NH 2 exhibits reversible luminescent mechanochromism between blue and cyan upon external mechanical stimulation and treatment with ethanol‐acetone (Figure 2b), which is caused by crystal‐to‐amorphous phase transitions. Moreover, Ag 18 bpy‐NH 2 also displays luminescent thermochromism with a linear relationship of the temperature to the intensity ratio of the dual emissions over a wide temperature range of 83 to 303 K (Figure 2c), which makes it a potential self‐calibrated molecular fluorescence thermometer …”