Structure–Property Relationships in Photoluminescent Bismuth Halide Organic Hybrid Materials

Abstract

Supporting InformationContents Synthesis of Bi-Halide-Organic Hybrid Materials.

Harnessing Bismuth Coordination Chemistry to Achieve Bright, Long-Lived Organic Phosphorescence

“…Consistent with previous literature, the Ln ions were found to incorporate at relatively low percentages that do not correspond to the amount added to the reaction mixture. 24 For the Eu-doped samples, Bi 1.98 Eu 0.02 -1 and Bi 1.8 Eu 0.2 -1, the incorporation of Ln ions is not linear with the reaction concentration because a 10-fold increase in the Eu concentration in the reaction mixture led to only a 3.4-fold increase in Eu in the structure.…”

“…Bi-based materials, in particular, are an attractive target for materials design. The global availability (i.e., low cost) and relatively low toxicity of Bi compared to other heavy elements, coupled with its unique lone-pair electron effects, flexible coordination geometries, and potential for structural regulation of the photophysical properties, are highly desirable. − Bi 3+ exhibits a closed-shell electron configuration like the d 10 metal ions, with the general electron configuration of n d 10 ( n + 1)­s 2 , making it amenable for achieving ligand-based emission in hybrid systems. − Indeed, the incorporation of heavy elements into π-conjugated materials is known to enhance the probability of accessing the triplet state of organic emitters, and hence phosphorescence, by increasing the rate of intersystem crossing (ISC). − The development of stable, long-lived phosphorescent emitters utilizing Bi may thus provide new design strategies for luminescent materials, with applications in light-emitting diodes and bioimaging. , Additionally, the broadband emission of Bi-based materials, coupled with the linelike emission of metals such as the Ln ions, provides further opportunities for dual emission, the possibility of color tuning, and/or white-light emission. − …”

On structural factors determining the nature of the fluorescent properties of OIHMs based on 8-hydroxyquinoline

“…Water molecules are known to quench the fluorescence due to possessing OH moieties with high-energy vibrations. 69,70 This water-assisted quenching mechanism originates in the fluorophore electronic excitation being resonantly transferred to the overtones and combination transitions of high-frequency stretching modes of the water molecules. The same effect is observed in the case of HgCl (2).…”

Synthetic Application of Bismuth LMCT Photocatalysis in Radical Coupling Reactions

“…Therein, the photolysis of BiCl 3 in benzene was studied, which resulted in the formation of chlorobenzene and bismuth metal under 290 nm irradiation . Over the years, investigations on the photochemical and photoluminescent behavior of different bismuth complexes have followed. However, it is important to note that the observed photochemical reactions were reported in the context of photodecomposition that have not been transferred to catalytic applications in organic synthesis.…”