Solvent-Mediated Separation and Reversible Transformation of 1D Supramolecular Polymorphs Built from [W₁₀O₃₂]^4-...

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 high-nuclearity silver-cluster-based one-dimensional (1D) polymorphs built from supramolecular synthon [W₁₀O₃₂@Ag₄₈(CyS)₂₄(NO₃)₁₆]·4NO₃ (Cy = cyclohexyl) bridged by four grouped inorganic NO₃^- 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 NO₃^- 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.