Three new Cu(i) based metal halides with excellent optical properties were developed by rational structural design, and a high-performance WLED was fabricated with the resulting material.

Improving the photoluminescence (PL) efficiency of organic luminescent molecules is still a great challenge. Herein, a novel zero-dimensional Sn­(IV)-based halide (C9H8N)2SnCl6 is prepared by assembling inactive quinoline cations and stable [SnCl6]2– polyhedra. Experimental characterizations and theoretical calculations show that the blue emission of (C9H8N)2SnCl6 centered at 433 nm is derived from the organic cations. Surprisingly, the PL efficiency of the as-prepared halide is nearly 50 times higher than that of the organic precursor and exhibits ultrahigh stability. Structural analysis shows that the introduction of inorganic clusters regulates the stacking mode of organic components and forms hydrogen bonds. This strong intermolecular interaction enhances the structural rigidity of (C9H8N)2SnCl6, inhibits concentration quenching and vibrational dissipation, and thus significantly improves the PL efficiency and stability of the organic cations. This work provides an important way to improve the PL performance and stability of organic species by constructing efficient intermolecular interactions.

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ns 2 -Metal halide perovskites have attracted wide attention due to their fascinating photophysical properties. However, achieving high photoluminescence (PL) properties is still an enormous challenge, and the relationship between the lattice environment and ns 2 -electron expression is still elusive. Herein, an organic−inorganic Bi 3+based halide (C 5 H 14 N 2 ) 2 BiCl 6 •Cl•2H 2 O (C 5 H 14 N 2 2+ = doubly protonated 1-methylpiperazine) with a six-coordinated structure has been successfully prepared, which, however, exhibits inferior PL properties due to the chemically inert expression of Bi 3+ -6s 2 lone-pair electrons. After reasonably embedding Sb 3+ with 5s 2 electrons into the lattice of (C 5 H 14 N 2 ) 2 BiCl 6 •Cl•2H 2 O, the host lattice environment induces the Sb−Cl moiety to change from the original five-coordinated to six-coordinated structure, thereby resulting in a broad-band yellow emission with a PL efficiency up to 50.75%. By utilizing the host lattice of (C 5 H 14 N 2 ) 2 BiCl 6 •Cl•2H 2 O, the expression of Sb 3+ -5s 2 lone-pair electrons is improved and thus promotes the radiative recombination from the Sb 3+ -3 P 1 state, resulting in the enhanced PL efficiency. This work will provide an in-depth insight into the effect of the local structure on the expression of Sb 3+ -5s 2 lone-pair electrons.