Cao Li-Hui, Li Hai-Yang, Xu Hong, Wei Yong-Li, Zang Shuang-Quan
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China.
Dalton Trans. 2017 Sep 12;46(35):11656-11663. doi: 10.1039/c7dt02697h.
Metal-organic frameworks (MOFs) with light-harvesting building blocks provide an excellent platform to study energy transfer in networks with well-defined structures. Here, we report the synthesis, dissolution-recrystallization structural transformation (DRST) and the Förster resonance energy transfer (FRET) properties of a 2D microporous MOF {[Cd(L)(Hdabco)]·5DMAc·6HO} (Cd-MOF, 1). Complex 1 can be dissolved in water and three other products with different dimensions recrystallized from the aqueous solution under diverse reaction conditions were obtained. Due to the porosity and excellent blue luminescence properties of complex 1, we also studied the FRET process between 1 and guest dyes. Two distinct organic dye molecules viz., acridine orange (AO) and rhodamine B (RhB), are encapsulated in 1 which has honeycomb-type nanochannels, and their influence on fluorescence emission has also been studied. The microporous complex 1 in (AO + RhB)@1 serves as an energy funnel that harvests high energy excitation and channels it onto AO and then onto RhB. The steady-state fluorescence and fluorescence dynamics of emission reveal successfully the process of stepwise vectorial energy transfer. Therefore, MOFs could be a class of promising host materials to be further explored in the field of energy transfer between MOF-host and organic guests.
具有光捕获结构单元的金属有机框架(MOF)为研究具有明确结构的网络中的能量转移提供了一个绝佳的平台。在此,我们报道了二维微孔MOF {[Cd(L)(Hdabco)]·5DMAc·6HO}(Cd-MOF,1)的合成、溶解-重结晶结构转变(DRST)以及Förster共振能量转移(FRET)性质。配合物1可溶于水,并在不同反应条件下从水溶液中重结晶得到了三种不同尺寸的其他产物。由于配合物1的孔隙率和优异的蓝色发光性质,我们还研究了1与客体染料之间的FRET过程。两种不同的有机染料分子,即吖啶橙(AO)和罗丹明B(RhB),被封装在具有蜂窝型纳米通道的1中,并且研究了它们对荧光发射的影响。(AO + RhB)@1中的微孔配合物1充当能量漏斗,收集高能激发并将其导向AO,然后再导向RhB。发射的稳态荧光和荧光动力学成功揭示了逐步矢量能量转移的过程。因此,MOF可能是一类有前途的主体材料,可在MOF主体与有机客体之间的能量转移领域中进一步探索。