Yin Hua-Qing, Chen Jia, Xue Yu-Wei, Ren Jing, Wang Xin-Hui, Fan Heng-Rui, Wei Shu-Yan, Sun Bo, Zhang Zhi-Ming
Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science & Engineering, School of Chemistry and Chemical Engineering, Tianjin University of Technology, 391 West Binshui Road, Tianjin, 300384, China.
Angew Chem Int Ed Engl. 2024 Dec 2;63(49):e202407596. doi: 10.1002/anie.202407596. Epub 2024 Nov 6.
Host-guest chemistry of chiral metal-organic frameworks (MOFs) has endowed them with circularly polarized luminescence (CPL), it is still limited for MOFs to systematically tune full-color CPL emissions and sizes. This work directionally assembles the chiral ligands, metal sites and organic dyes to prepare a series of crystalline enantiomeric D/L-Cd/Zn-n MOFs (n=1~5, representing the adding amount of dyes), where D/L-Cd/Zn with the formula of Cd(D/L-Cam)(TPyPE) and Zn(D/L-Cam)(TPyPE) (D/L-Cam=D/L-camphoric acid, TPyPE=4,4',4'',4'''-(1,2-henediidenetetra-4,1-phenylene)tetrakis[pyridine]) were used as the chiral platforms. The framework-dye-enabled emission and through-space chirality transfer facilitate D/L-Cd/Zn-n bright full-color CPL activity. The ideal yellow CPL of D-Cd-5 and D-Zn-4, with |g| as 4.9 × 10 and 1.3×10 and relatively high photoluminescence quantum yield of 40.79 % and 45.40 %, are further assembled into a white CPL light-emitting diode. The crystal sizes of D/L-Cd/Zn-n were found to be strongly correlated to the types and additional amounts of organic dyes, that the positive organic dyes allow for the preparation of > 7 mm bulks and negative dyes account for sub-20 μm particles. This work opens a new avenue to fabricate full-color emissive CPL composites and provides a potentially universal method for controlling the size of optical platforms.
手性金属有机框架(MOF)的主客体化学赋予了它们圆偏振发光(CPL)特性,但MOF系统地调节全色CPL发射和尺寸仍然受到限制。这项工作定向组装手性配体、金属位点和有机染料,制备了一系列结晶对映体D/L-Cd/Zn-n MOF(n = 1~5,表示染料的添加量),其中化学式为Cd(D/L-Cam)(TPyPE)和Zn(D/L-Cam)(TPyPE)(D/L-Cam = D/L-樟脑酸,TPyPE = 4,4',4'',4'''-(1,2-己二亚基四-4,1-亚苯基)四吡啶)的D/L-Cd/Zn用作手性平台。框架-染料引发的发射和空间手性转移促进了D/L-Cd/Zn-n的明亮全色CPL活性。D-Cd-5和D-Zn-4的理想黄色CPL,|g|分别为4.9×10和1.3×10,相对较高的光致发光量子产率分别为40.79%和45.40%,进一步组装成白色CPL发光二极管。发现D/L-Cd/Zn-n的晶体尺寸与有机染料的类型和添加量密切相关,正性有机染料可制备>7毫米的块状物,负性染料则形成小于20微米的颗粒。这项工作为制造全色发射CPL复合材料开辟了一条新途径,并为控制光学平台的尺寸提供了一种潜在的通用方法。