Solvent-Mediated Separation and Reversible Transformation of 1D Supramolecular Polymorphs Built from [W₁₀O₃₂]^4– Templated 48-Nuclei Silver(I) Cluster

Abstract

Although the C−H•••O interaction is an essential component in determining the molecular packing in solids and the properties in supramolecular chemistry, it presents a significant challenge when trying to use it in the crystal engineering of complex metallosupramolecules, even though it is a relatively weak supramolecular force. The first pair of highnuclearity silver-cluster-based one-dimensional (1D) polymorphs built from supramolecular synthon [W 10 O 32 @Ag 48 (CyS) 24 (NO 3 ) 16 ]•4NO 3 (Cy = cyclohexyl) bridged by four grouped inorganic NO 3 − ligands is initially synthesized as a mixed phase and further individually crystallized as a pure phase by virtue of tuning intermolecular C−H•••O interaction through altering the composition ratio of ternary solvent system. Increasing highly polar and hydrogen-bonding methanol strengthens the solvation effect reflected by the change of coordination orientation of surface NO 3 − ligands, which dominates the packing of the 1D chains in the crystal lattice, resulting in the crystallization of polymorphs from tetragonal to monoclinic. The two crystalline forms can also be reversibly transformed to each other in an appropriate solvent system. Correspondingly, the two polymorphs display distinct temperature-dependent photoluminescence behaviors, which are ascribed to the variation of noncovalent interchain C−H••• O interactions along with the temperature. More importantly, benefiting from the suppression of fluorescence, both polymorphs offer excellent photothermal conversion properties which were further applied to remote-controlled laser ignition. These findings may open more avenues for the application of solvent-mediated intermolecular interaction in controlling the molecule arrangement as well as the optical properties.

All-catecholate-stabilized black titanium-oxo clusters for efficient photothermal conversion

“…Generally, energy transitions in photophysical processes are primarily depicted by the Jablonski diagram, which includes the following procedures: excitation (or absorption), vibrational relaxation (heat release), radiative emission (fluorescence), and non-radiative transition (heat release). 63–65 No fluorescence was observed for Ti2 , Ti8 , and Ti16 . Therefore, absorption must be considered as the primary factor influencing photothermal conversion performance.…”

A concise guide to chemical reactions of atomically precise noble metal nanoclusters

“…Recently, Sheng et al reported the first supramolecular polymorphs of high-nuclearity Ag 48 NCs encapsulated in an anionic template via solvent mediation. 266…”

Solvent-Mediated Hetero/Homo-Phase Crystallization of Copper Nanoclusters and Superatomic Kernel-Related NIR Phosphorescence

“…Solvents, act as crucial reaction participant in the wet synthesis of metal nanoclusters, with their roles being empirically summarized into two key aspects: (1) the solvation interaction between solvents and precursors governs the formation of nanocluster species; and (2) subsequent desolvation processes guide crystallization behaviors, playing a pivotal role in both the formation and crystallization of metal nanoclusters. − Therefore, the design and fabrication of solvent-mediated superatomic Cu NCs are significantly important for gaining in-depth understanding of the solvation effect that dominates their assembly process and subsequent crystallization outcomes.…”