Zhang Chong, Yan Zhi-Ping, Dong Xi-Yan, Han Zhen, Li Si, Fu Ting, Zhu Yan-Yan, Zheng You-Xuan, Niu Yun-Yin, Zang Shuang-Quan
Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Adv Mater. 2020 Sep;32(38):e2002914. doi: 10.1002/adma.202002914. Epub 2020 Aug 16.
The host-guest chemistry of metal-organic frameworks (MOFs) has enabled the derivation of numerous new functionalities. However, intrinsically chiral MOFs (CMOFs) with helical channels have not been used to realize crystalline circularly polarized luminescence (CPL) materials. Herein, enantiomeric pairs of MOF crystals are reported, where achiral fluorophores adhere to the inner surface of helical channels via biology-like H-bonds and hence inherit the helicity of the host MOFs, eventually amplifying the luminescence dissymmetry factor (g ) of the host l/d-CMOF (±1.50 × 10 ) to a maximum of ±0.0115 for the composite l/d-CMOF⊃fluorophores. l/d-CMOF⊃fluorophores in pairs generate bright color-tunable CPL and almost ideal white CPL (0.33, 0.32) with a record-high photoluminescence quantum yield of ≈30%, which are further assembled into a white circularly polarized light-emitting diode. The present strategy opens a new avenue for propagating the chirality of MOFs to realize universal chiroptical materials.
金属有机框架材料（MOFs）的主客体化学性质已催生出众多新功能。然而，具有螺旋通道的本征手性MOFs（CMOFs）尚未被用于实现晶体圆偏振发光（CPL）材料。在此，报道了MOF晶体的对映体对，其中非手性荧光团通过类似生物的氢键附着在螺旋通道的内表面，从而继承主体MOFs的螺旋性，最终将主体l/d-CMOF（±1.50×10）的发光不对称因子（g）放大至复合l/d-CMOF⊃荧光团的最大值±0.0115。成对的l/d-CMOF⊃荧光团产生明亮的颜色可调CPL和几乎理想的白色CPL（0.33，0.32），光致发光量子产率创纪录地高达约30%，这些荧光团进一步组装成白色圆偏振发光二极管。目前的策略为传播MOFs的手性以实现通用手性光学材料开辟了一条新途径。
