Zhang Shuai, Wang Lei, Wang Yilan, Wang Xiaoming, Ye Shi
State Key Lab of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques, School of Materials Science and Engineering, South China University of Technology, 510641 Guangzhou, China.
Condensed Matter and Interfaces, Debye Institute for Nanomaterials Science, Utrecht University, 3508 TA Utrecht, The Netherlands.
J Phys Chem Lett. 2023 Aug 31;14(34):7773-7779. doi: 10.1021/acs.jpclett.3c02139. Epub 2023 Aug 24.
Photoinduced self-trapped exciton emission is common in soft matter metal halide semiconductors, whereas analogous phenomena in metal halide insulators with localized emitting centers and delayed satellite emission have rarely been identified. In this study, a new zero-dimensional Mn(II) hybrid of [3DPTPP]MnBr (3DPTPP = (3-(dimethylamino)propyl)(triphenyl)phosphonium) with only one crystallographic Mn site but dual emission is reported. The delayed red emission (∼630 nm) is successfully assigned to a satellite of the green-emissive (∼530 nm) MnBr tetrahedron shifted by N-H vibration (∼2500 cm), directly evidenced by the Raman spectra and further supported by density functional theory calculation. The photoluminescence decay curves demonstrate their same origin, but the red emission exhibits a delayed process. The temperature- and pressure-dependent PL spectra, temperature-dependent distortion of the MnBr tetrahedron, and light polarization spectra confirmed the consistency and distinctness of the dual emission. This study will inspire further research on self-trapped optoelectronic processes in soft metal halides.
光致自陷激子发射在软物质金属卤化物半导体中很常见，而在具有局域发射中心和延迟卫星发射的金属卤化物绝缘体中，类似现象却很少被发现。在本研究中，报道了一种新型的零维[3DPTPP]MnBr（3DPTPP =（3-（二甲基氨基）丙基）（三苯基）鏻）锰（II）配合物，它只有一个晶体学锰位点，但具有双重发射。延迟的红色发射（630 nm）成功归因于绿色发射（530 nm）的MnBr四面体的卫星发射，其因N-H振动（~2500 cm）而发生位移，拉曼光谱直接证明了这一点，并得到密度泛函理论计算的进一步支持。光致发光衰减曲线表明它们具有相同的起源，但红色发射呈现出延迟过程。温度和压力依赖的PL光谱、MnBr四面体的温度依赖畸变以及光偏振光谱证实了双重发射的一致性和独特性。这项研究将激发对软金属卤化物中自陷光电子过程的进一步研究。
