Zhang Shuai, Han Kai, Xia Zhiguo
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.
Angew Chem Int Ed Engl. 2025 Feb 10;64(7):e202419333. doi: 10.1002/anie.202419333. Epub 2024 Dec 4.
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, (RPhP)MnBrNCS (R=phenyl, pentyl or methyl; PhP=triphenylphosphine; x=1-3), achieved by gradually substituting bromides with pseudohalides (NCS). Compared to the green-emitting AMnBr (512 nm), the mixed hybrids exhibit significantly distorted [MnBrNCS] 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.
基于锰(II)的卤化物最近作为用于各种光子应用的新兴发光材料引起了极大的关注。一般来说,具有四面体配位的锰(II)杂化物呈现绿色发射,然而,具有八面体配位的杂化物则发出红色发射。在此,我们设计合成了四面体锰(II)拟卤化物杂化物(RPhP)MnBrNCS(R = 苯基、戊基或甲基;PhP = 三苯基膦;x = 1 - 3),通过用拟卤化物(NCS)逐渐取代溴化物来实现。与发出绿色光的AMnBr(512 nm)相比,混合杂化物表现出具有高偶极矩的明显扭曲的[MnBrNCS]四面体,从而导致明显的斯托克斯位移能量和在549 - 613 nm范围内明显的红移发射。此外,这些杂化物的光致发光量子产率(PLQY)与锰(II)离子的对相关函数密切相关,特别是锰···锰的距离。这些发现突出了偶极矩在决定发射特性方面的关键作用,并扩展了锰(II)拟卤化物杂化物的发光家族。