Liu Jinjian, Li Jing, Lu Wenbo
Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, The School of Chemical and Material Science, Shanxi Normal University Linfen 041004 China
RSC Adv. 2019 Oct 17;9(57):33155-33162. doi: 10.1039/c9ra06703e. eCollection 2019 Oct 15.
Viologen units have been widely used to impart metal-organic frameworks (MOFs) with photochromic properties. However, construction of a stable photochromic system in viologen MOFs has not been fully explored. Herein, we report three examples of MOFs, namely, {[Cd(CEbpy)(-BDC)(DMF)]·2HO} (1), {[Cd(CEbpy)(-BDC)(HO)]·HO} (2), and {[Zn(CEbpy)(-HBDC)(-BDC)]·HO} (3) based on benzenedicarboxylic acids (-HBDC = 1,3-benzenedicarboxylic acid, -HBDC = 1,4-benzenedicarboxylic acid) and a viologen-derived ligand 1-carboxyethyl-4,4'-bipyridine (L = CEbpy). As expected, the incorporation of the viologen unit into the frameworks results in the predefined photochromism upon both sunlight and UV-light. Compounds 1-3 feature a two-dimensional (2D) layered structure and are all photochromic due to the formation of CEbpy radicals by photoinduced electron transfer (PET). The aggregates build an interesting stable crystalline framework that exhibits long-lived color constancy in the solid state.
紫精单元已被广泛用于赋予金属有机框架(MOF)光致变色特性。然而,在紫精MOF中构建稳定的光致变色体系尚未得到充分探索。在此,我们报道了三个基于苯二甲酸(-HBDC = 1,3 - 苯二甲酸,-HBDC = 1,4 - 苯二甲酸)和一种紫精衍生配体1 - 羧乙基 - 4,4'- 联吡啶(L = CEbpy)的MOF实例,即{[Cd(CEbpy)(-BDC)(DMF)]·2H₂O} (1)、{[Cd(CEbpy)(-BDC)(H₂O)]·H₂O} (2)和{[Zn(CEbpy)(-HBDC)(-BDC)]·H₂O} (3)。正如预期的那样,将紫精单元引入框架中会导致在阳光和紫外光下都出现预定义的光致变色现象。化合物1 - 3具有二维(2D)层状结构,并且由于光致电子转移(PET)形成CEbpy自由基而都具有光致变色性。这些聚集体构建了一个有趣的稳定晶体框架,该框架在固态下表现出长寿命的颜色稳定性。