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While a number of highly luminescent copper­(I) halide based hybrid materials built on coordinate bonds (Cu–L; L = N, P, S-based ligands) have been obtained, the poor structural stability largely limited their commercialization. In contrast, according to the previous studies, the ionic structures (L-free) are more stable than those built on Cu–L coordinate bonds. However, the extremely weak emission hinders their optical applications. Herein, we report a tetra-alkylammonium-cation-induced strategy for the synthesis of stable and highly luminescent ionic CuBr-based hybrid materials. It is interesting to find that the tetra-alkylammonium cations with different chains could induce diverse CuBr-based anions. Moreover, most of these CuBr-based hybrids are highly luminescent, which makes them promising candidates as an alternative to phosphors and with potential applications in sensing.

A pair of enantiomerically pure metallosquares based on linear platinum-diacetylene edges and tribenzotriquinacene corner units was synthesized. Their structures were characterized by (1) H-, (13) C- and (31) P NMR spectroscopy as well as MALDI-TOF mass spectrometry and circular dichroism. Based on DFT calculation, the optimized geometry possesses a distorted square conformation in which the four edges are not sitting on the same plane. The molecular square further self-assembled in the solid state to afford microspheres with diameter of approximately 300 nm, as determined by scanning electron microscopy.