s-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 s-electron expression is still elusive. Herein, an organic-inorganic Bi-based halide (CHN)BiCl·Cl·2HO (CHN = 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-6s lone-pair electrons. After reasonably embedding Sb with 5s electrons into the lattice of (CHN)BiCl·Cl·2HO, 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 (CHN)BiCl·Cl·2HO, the expression of Sb-5s lone-pair electrons is improved and thus promotes the radiative recombination from the Sb-P 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-5s lone-pair electrons.
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http://dx.doi.org/10.1021/acs.inorgchem.2c03961 | DOI Listing |
J Phys Chem Lett
January 2025
Beijing National Laboratory for Molecular Science (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Clusters serve as the optimal model to elucidate the structure-property relationship of materials, bridging condensed matter and individual atoms. The pursuit of exceptionally stable clusters has garnered significant interest. The distinctive electronic configuration and symmetrical geometry generally provide a consistent rationale for their stability.
View Article and Find Full Text PDFChem Biomed Imaging
December 2024
College of Chemistry and Materials Science, Jinan University, Guangzhou, Guangdong 510632, China.
The large-scale preparation of fluorescent nanomaterials with laboratory-relevant chemical and optical properties will greatly forward their consumer market applications; however, it still remains challenging. In this work, a universal strategy was developed for the rapid and large-scale synthesis of fluorescent sulfur quantum dots that recently has drawn great attention because of their unique optical characteristics. From the fact that empty 3d orbitals of sulfide species are able to bind with lone-pair π electrons of the heteroatomic groups, many amino-group containing compounds, such as amino acid and polyethylenimine molecules, were exploited to synthesize sulfur quantum dots.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
Aromatic organometallic complexes, such as ferrocene and the "inverse sandwich complex" [NaCp], are stabilized via charge-transfer (C-T) interactions and cation-π interactions (i.e., charge-induced dipole and charge-quadrupole interactions).
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen, Guangdong 518055, China.
Lone-pair expression is significantly influenced by geometric constraints in hybrid metal halides (HMHs). Two-dimensional (2D) HMHs possess reduced structural dimensionality, allowing for a wide range of off-center displacement of the metal center. However, the effect of lone-pair-induced off-center distortion on the geometric configuration of inorganic units, electronic properties, and exciton emissions in 2D HMHs remains unclear.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Soochow University, College of Chemistry, Chemical Engineering and Materials Science, Ren-ai Road 199#, Industry Park, 215123, Suzhou, CHINA.
The rapid reaction between lead iodide (PbI2) and formamidinium iodide (FAI) complicates the fabrication of high-quality formamidinium lead iodide (FAPbI3) films. Conventional methods, such as using nonvolatile small molecular additives to slow the reaction, often result in buried interfacial voids and molecule diffusion, compromising the devices' operational stability. In this study, we introduced a molecular "thruster"-a hypervalent iodine (III) compound with three carbonyl groups and a C--I⁺ bond-that possesses coordination and dissociation abilities, enabling programed modulation of perovskite-film growth kinetics.
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