Organolead Halide-Based Coordination Polymers: Intrinsic Stability and Photophysical Applications.

ConspectusOrganolead halide-based photovoltaics are one of the state-of-the-art solar cell systems with efficiencies increasing to 25% over the past decade, ascribed to their high light-absorption coefficient, broad wavelength coverage, tunable band structure, and excellent carrier mobility. Indeed, these optical characteristics are highly demanding in photocatalysis and photoluminescence (PL), which also involve the solar energy utilization and charge transport. However, the vast majority of organolead halides are ionically bonded structures and susceptible to degradation upon high-polarity protic molecules (e.g., water (vapor) and alcohol), which are often inevitable in many photochemical applications. Encapsulation is a commonly used stabilization approach by coating protective layers, avoiding the direct contact between organolead halides and polar molecules. However, this may partially hinder the light penetration to the inner hybrid halide materials, and introduce new interface problems that are important in photocatalysis and luminescent sensing. Therefore, developing intrinsically stable organometal halide hybrids is a major target for their applications in optoelectronic applications.In this Account, recent research progress on the synthesis of organolead halide-based coordination polymers for a variety of photoactive applications is described. Herein, we propose a general strategy to advance the intrinsic stability of organometal halide crystalline materials by using coordinating anionic organic linkers, which occupy the excellent photophysical features analogous to those of perovskites. Unlike the organoammonium cations as for ionically bonded structures, the anionic structure-directing agents (e.g., organocarboxylates) render well-defined metal-carboxylate coordination motifs in extended architectures spanning from low-dimensional (0D, 1D) to high-dimensional cationic inorganic Pb-X-Pb (X = F/Cl/Br/I) sublattices. This family of organolead halide coordination polymers can endure chemically reactive environments over a wide range of pH and aqueous boiling condition, which have been systematically investigated by experimental studies and theoretical calculations. Many chloride/bromide-based coordination polymers show air-stable, broadband self-trapped emission with large Stokes shift and high color rendition, exhibiting the absolute quantum yields of 35-72%. Among them, the porous frameworks with low-dimensional (0D, 1D) inorganic blocks are recognized as a rare class of porous metal-organic frameworks (MOFs) constructed by lead halides as secondary building units (SBUs). They not only occupy substantially higher light-harvesting and carrier-transport properties than conventional metal oxide-based MOFs, but also allow for isoreticular modification to regulate the PL characteristics by guest molecules. More importantly, combining the high stability with excellent carrier characteristics, a layered organolead iodide coordination polymer shows the overall photocatalytic water splitting without the use of any sacrificial agent under simulated sunlight illumination. Given the wide choice of structurally diverse organocarboxylate linkers, we hope this Account provides deep insights on the importance of coordination chemistry in the discovery of a wide family of intrinsically stable organolead halides to expand their photophysical applications.