Hydrogen bonding evolution and efficient blue light emission in a series of Zn-based organic-inorganic hybrid metal halide crystals  

一系列锌基有机-无机杂化金属卤化物晶体中的氢键演变和高效蓝光发射

作　　者：Qi Zhang Tianwen Huang Zheyuan Liu Ya-Nan Feng Yan Yui Lingyun Li 张琪;黄天文;刘哲源;冯亚南;于岩;李凌云

机构地区：[1]Key Laboratory of Advanced Materials Technologies,International(Hong Kong Macao and Taiwan)Joint Laboratory on Advanced Materials Technologies,College of Materials Science and Engineering,Fuzhou University,Fuzhou 350108,China

出　　处：《Science China Materials》2025年第4期1004-1011,共8页中国科学(材料科学)(英文版)

基　　金：supported by the National Natural Science Foundation of China(51972061,U1905215);the National Key Research and Development Program of China(2020YFA0710303);the Natural Science Foundation of Fujian Province,China(2022J01088)。

摘　　要：The influence of hydrogen bonding on spectroscopic properties is one of the fundamental issues in the field of luminescent organic-inorganic hybrid metal halides(OIMHs).We design and prepare three OIMHs,namely,crystals 1,2 and 3,using 2,2′-bipyridine and ZnCl2 as starting materials.From crystals 1 to 3,the hydrogen bonding environment surrounding the 2,2′-bipyridinium cations gradually weakens,with both the dihedral angle and the number of hydrogen bonds around them decreasing progressively.Correspondingly,the blue emission belonging to the S1→S0 transition of the three crystals gradually increases,with crystal 3 exhibiting the strongest blue light emission and a photo-luminescence quantum yield reaching 34.10%.In crystal 1,the dense hydrogen bonding environment of the 2,2′-bipyridinium cation results in an obvious energy transfer from S1 to T1.This reduces the population of the S1 state,thereby leading to weaker blue light emission.In crystals 2 and 3,the weaker hydrogen bonding environment and smaller spatial distortion of organic cations weaken or even prevent energy transfer between S1 and T1,thereby enhancing blue light emission.These findings provide new insights for exploring novel luminescent OIMHs and developing more effective means of regulating their luminescence performance.氢键对晶体光致发光性能的影响是发光有机-无机杂化金属卤化物(OIMHs)领域的基本问题之一.我们以2,2′-联吡啶和ZnCl2为原料,设计并制备了三种OIMH,即晶体1、2和3.从晶体1到晶体3,2,2′-联吡啶阳离子周围的氢键环境逐渐减弱,二面角和周围的氢键数量都逐渐减少.相应地,三种晶体的S1→S0跃迁的蓝光发射逐渐增加,其中晶体3表现出最强的蓝光发射,光致发光量子产率达到34.10%.在晶体1中,2,2′-联吡啶阳离子的密集氢键环境导致从S1到T1的明显能量转移.这减少了S1态的布局数,从而导致蓝光发射减弱.而在晶体2和3中,较弱的氢键环境和较小的有机阳离子空间畸变削弱甚至阻止了S1和T1之间的能量传递,从而增强了蓝光发射.研究结果将为探索新型发光OIMHs和开发更有效的调节发光性能的方法提供新的见解.

关 键 词：optical materials PHOTOLUMINESCENCE blue emission organic-inorganic hybrid metal halides hydrogen bonding 

分 类 号：O641[理学—物理化学]