Pseudohalide Anions Driven Structural Modulation in Distorted Tetrahedral Manganese(II) Hybrids toward Tunable Green-Red Emissions

Shuai Zhang; Kai Han; Zhiguo Xia

doi:10.1002/anie.202419333

Pseudohalide Anions Driven Structural Modulation in Distorted Tetrahedral Manganese(II) Hybrids toward Tunable Green-Red Emissions

Angew Chem Int Ed Engl. 2024 Nov 26:e202419333. doi: 10.1002/anie.202419333. Online ahead of print.

Authors

Shuai Zhang¹, Kai Han¹, Zhiguo Xia²

Affiliations

¹ SCUT: South China University of Technology, State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques, Guangdong Engineering Technology Research and Development Centre of Special Optical Fiber Materials and Devices, School of Physics and Optoelectronics, South China University of Technology, Guangzhou, 510641 China, CHINA.
² South China University of Technology, State Key Lab of luminescence materials, State Key Laboratory of Luminescent Materials and Devices, Wushan Road 381, Guangzhou 510641, China, 510641, Guangzhou, CHINA.

PMID: 39588634
DOI: 10.1002/anie.202419333

Abstract

Mn(II)-based halides have recently garnered significant interest as emerging luminescence materials for diverse photonic applications. Generally, Mn(II) hybrids with tetrahedral coordination show green emission, however, ones with octahedral coordination give red emission. Herein, we design the synthesis of tetrahedral Mn(II) pseudohalide hybrids, (RPh3P)2MnBrxNCS4-x (R= phenyl, pentyl or methyl; Ph3P = triphenylphosphine; x = 1 - 3), achieved by gradually substituting bromides with pseudohalides (NCS-). Compared to the green-emitting A2MnBr4 (512 nm), the mixed hybrids exhibit significantly distorted [MnBrxNCS4-X] tetrahedra with high dipole moment, thus leading to the distinct Stokes shift energies and noticeable red shift emission in the range of 549 ~ 613 nm. Furthermore, the photoluminescence quantum yield (PLQY) of these hybrids correlates strongly with the pair correlation function of Mn(II) ions, specifically the Mn···Mn distance. These findings highlight the critical role of dipole moments in determining the emission properties and expand the luminescent family of Mn(II) pseudohalide hybrids.

Keywords: Distorted tetrahedra; Mn(II) Pseudohalide hybrids; Spectral modulation; dipole moment; photoluminescence.