Structure–Property Relationships in Photoluminescent Bismuth Halide Organic Hybrid Materials

Seven novel bismuth(III)-halide phases, Bi2Cl6(terpy)2·0.5(H2O) (1), Bi2Cl4(terpy)2(k2-TC)2(2) (TC = 2-thiophene monocarboxylate), BiCl(terpy)(k2-TC)2 (3A-Cl), BiBr(terpy)(k2-TC)2 (3A-Br), (3B-Cl), [BiCl(terpy)(k2-TC)2][Bi(terpy)(k2-TC)3]·0.55(TCA) (4), [BiBr3(terpy)(MeOH)] (5), and [BiBr2(terpy)(k2-TC)][BiBr1.16(terpy)(k2-TC)1.84] (6), were prepared under mild synthetic conditions from methanolic/aqueous solutions containing BiX3 (X Cl, Br) 2,2′:6′,2″-terpyridine (terpy) and/or monocarboxylic acid (TCA). A heterometallic series, 3A-Bi1–xEuxCl, with the general formula Bi1–xEuxCl(terpy)(k2-TC)2 (x 0.001, 0.005, 0.01, 0.05) was also through trace Eu doping of 3A-Cl phase. The structures determined single-crystal X-ray diffraction are built a range molecular units including monomeric dimeric complexes. solid-state photoluminescent properties compounds examined steady-state time-resolved methods. While homometallic phases exhibited broad green to yellow emission, displayed yellow, orange, red emission that can be attributed simultaneous ligand/Bi-halide centered emissions. Photoluminescent color tuning achieved by controlling relative intensities these concurrent emissions compositional modifications percentage. Notably, all emissive homo- rare visible excitation pathways based on theoretical quantum mechanical calculations halide-metal ligand charge transfer (XMLCT). Through combined experimental computational approach, fundamental insight into structure–property relationships within Bi halide organic hybrid materials is provided.