Supramolecular isomerism between cyclodimeric and sinusoidal 1D coordination polymers: competition of tunable argentophilic vs. electrostatic interactions

Abstract

Systematic supramolecular isomerism between metallacyclodimeric species and sinusoidal 1D coordination polymers was observed. Slow diffusion of AgX (X⁻ = NO₃⁻, BF₄⁻, ClO₄⁻, and PF₆⁻) with 1,3-bis(dimethyl(pyridin-4-yl)silyl)propane afforded 28-membered metallacyclodimers [AgL]₂(X)₂ with argentophilic, electrostatic, and π–π interactions that are very sensitive to the bite size of each anion in the crystalline state. Successive anion exchange of [Ag(L)]₂(NO₃)₂ with X⁻ (X⁻ = BF₄⁻, ClO₄⁻, and PF₆⁻) crystallized in situ, resulting in a systematic supramolecular isomerization to sinusoidal 1D coordination polymers in mother liquor. In the following pages, the different photophysical properties between the metallacyclodimeric species and the sinusoidal 1D coordination polymers on some solvent adsorption are discussed based on the photoluminescence (PL) spectra.