Solvent-modulated zinc^II networks with different stacking arrangements

<div><p>Two Zn^II complexes, [Zn₂(L)₂(DMF)(H₂O)₂]·DMF (<b>1</b>) and [Zn(L)(DEF)]·DEF (<b>2</b>), were synthesized by solvothermal reactions using 4,4′-(2,3,5,6-tetramethylbenzene1,4-diyl)dibenzoic acid (H₂L) and Zn(NO₃)₂·6H₂O in different solvents of DMF, ethanol, and water for <b>1</b> and N,N-diethylformamide (DEF) for <b>2</b>. The L²⁻ with different coordination modes connect [Zn₂(COO)₂] secondary building units (SBUs) to generate a wavy 2-D (4,4) network of <b>1</b> while in <b>2</b> there are paddlewheel [Zn₂(COO)₄] SBUs which are connected by L²⁻ to form a planar 2-D (4,4) network. The 2-D layered structures show different stacking arrangements and are further linked by hydrogen bonding or C–H⋯π interactions to give 3-D architectures. The different structures and stacking arrangements of <b>1</b> and <b>2</b> result from different reaction solvents. Photoluminescence properties of the complexes were investigated.</p>