Ren Daming, Xia Hai-Lun, Zhou Kang, Wu Shenjie, Liu Xiao-Yuan, Wang Xiaotai, Li Jing
Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic, 7098 Liuxian Blvd, Nanshan District, Shenzhen, 518055, People's Republic of China.
Department of Chemistry, University of Colorado Denver, Campus Box 194, P. O. Box 173364, Denver, Colorado, 80217-3364, USA.
Angew Chem Int Ed Engl. 2021 Nov 15;60(47):25048-25054. doi: 10.1002/anie.202110531. Epub 2021 Oct 18.
While limited choice of emissive organic linkers with systematic emission tunability presents a great challenge to investigate energy transfer (ET) over the whole visible light range with designable directions, luminescent metal-organic frameworks (LMOFs) may serve as an ideal platform for such study due to their tunable structure and composition. Herein, five Zr cluster-based LMOFs, HIAM-400X (X=0, 1, 2, 3, 4) are prepared using 2,1,3-benzothiadiazole and its derivative-based tetratopic carboxylic acids as organic linkers. The accessible unsaturated metal sites confer HIAM-400X as a pristine scaffold for linker installation. Six full-color emissive 2,1,3-benzothiadiazole and its derivative-based dicarboxylic acids (L) were successfully installed into HIAM-400X matrix to form HIAM-400X-L, in which the ET can be facilely tuned by controlling its direction, either from the inserted linkers to pristine MOFs or from the pristine MOFs to inserted linkers, and over the whole range of visible light. The combination of the pristine MOFs and the second linkers via linker installation creates a powerful two-dimensional space in tuning the emission via ET in LMOFs.
虽然具有系统发射可调性的发光有机连接体选择有限，这给在整个可见光范围内以可设计方向研究能量转移（ET）带来了巨大挑战，但发光金属有机框架（LMOF）因其可调的结构和组成，可能成为此类研究的理想平台。在此，使用2,1,3 - 苯并噻二唑及其衍生物基四齿羧酸作为有机连接体，制备了五种基于Zr簇的LMOF，即HIAM - 400X（X = 0, 1, 2, 3, 4）。可及的不饱和金属位点使HIAM - 400X成为用于连接体安装的原始支架。六种全色发光的2,1,3 - 苯并噻二唑及其衍生物基二羧酸（L）成功安装到HIAM - 400X基质中，形成HIAM - 400X - L，其中通过控制能量转移方向，无论是从插入的连接体到原始金属有机框架，还是从原始金属有机框架到插入的连接体，并且在整个可见光范围内，都可以轻松调节能量转移。通过连接体安装将原始金属有机框架与第二连接体相结合，在通过LMOF中的能量转移调节发射方面创造了一个强大的二维空间。
