The complexes of transition metal atoms like Fe, Ru, Pd, Pt, Cu, Au, Ag, Os, Zn have been the focus of the scientific community for the application in photophysics and photochemistry. These transition metal-based complexes are well explored and have been commercialized, however, many of these metal atoms are highly expensive, toxic, and suffer from various other problems. Due to these reasons a non-toxic and easily available substitute which can mimic the photophysical efficiency of the these metals is highly required. Therefore, to overcome these issues, herein we show that main group metal, Bismuth, can be used to replace such transition metals. We report the fundamental photophysical properties of a series of phenanthroline substituted complexes of BiCl3, BiBr3 and BiI3. The complexes of different coordination number (7 and bi-octahedron) are synthesized and characterized using various spectroscopic tools. All the complexes vary by different number of halogen(s) and ligands bound to bismuth(III) centre, hence affecting the photophysical properties of the complexes. In this work we present the design strategy to synthesize novel bismuth (Bi) coordination complexes and explored their fundamental photophysical properties for applications in solar light absorption and light emission. We developed the complexes with different coordination bonds and varying electronic density along the bismuth atom. The analysis of the experimental and theoretical studies show that excited state photophysical properties of the complexes remain unchanged by switching the coordination geometry of the complexes as well as the electronic density by varying the ancillary ligands. However, the detailed ground state photophysical studies along with theoretical analysis proves that one coordination geometry with specific ancillary ligand leads to strong absorption of visible light, hence favour applications in photovoltaics. The combined comparative studies illustrate a design principle to develop novel bismuth coordination complexes with different varying properties by tuning the electron donating tendency of the ancillary ligands.

Photophysical studies of bismuth based coordination complexes for panchromatic solar light absorbtion

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