Dhara Barun, Nagarkar Sanjog S, Kumar Jitender, Kumar Vikash, Jha Plawan Kumar, Ghosh Sujit K, Nair Sunil, Ballav Nirmalya
Department of Chemistry, Indian Institute of Science Education and Research (IISER) , Pashan, Pune 411008, India.
Department of Physics, Indian Institute of Science Education and Research (IISER) , Pashan, Pune 411008, India.
J Phys Chem Lett. 2016 Aug 4;7(15):2945-50. doi: 10.1021/acs.jpclett.6b01236. Epub 2016 Jul 19.
Redox-active pyrrole (Py) monomers were intercalated into 1D nanochannels of [Cd(NDC)0.5(PCA)]·Gx (H2NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) (1) - a fluorescent 3D MOF (λem = 385 nm). Subsequent activation of 1⊃Py upon immersing into iodine (I2) solution resulted in an increment of the bulk electrical conductivity by ∼9 orders of magnitude. The unusual increase in conductivity was attributed to the formation of highly oriented and conducting polypyrrole (PPy) chains inside 1D nanochannels and specific host-guest interaction in 1⊃PPy thereof. The Hall-effect measurements suggested 1⊃PPy to be an n-type semiconductor material with remarkably high-carrier density (η) of ∼1.5 × 10(17) cm(-3) and mobility (μ) of ∼8.15 cm(2) V(-1) s(-1). The fluorescence property of 1 was almost retained in 1⊃PPy with concomitant exciplex-type emission at higher wavelength (λem = 520 nm). The here-presented results on [MOF⊃Conducting Polymer] systems in general will serve as a prototype experiment toward rational design for the development of highly conductive yet fluorescent MOF-based materials for various optoelectronic applications.
氧化还原活性吡咯（Py）单体被插入到[Cd(NDC)0.5(PCA)]·Gx（H2NDC = 2,6-萘二甲酸，HPCA = 4-吡啶甲酸，G =客体分子）（1）的一维纳米通道中——一种荧光三维金属有机框架（λem = 385 nm）。将1⊃Py浸入碘（I2）溶液中进行后续活化，导致整体电导率增加了约9个数量级。电导率的异常增加归因于在一维纳米通道内形成了高度取向的导电聚吡咯（PPy）链以及其1⊃PPy中的特定主客体相互作用。霍尔效应测量表明1⊃PPy是一种n型半导体材料，其载流子密度（η）非常高，约为1.5×10(17) cm(-3)，迁移率（μ）约为8.15 cm(2) V(-1) s(-1)。1的荧光特性在1⊃PPy中几乎得以保留，同时在更高波长（λem = 520 nm）处伴有激基复合物型发射。这里展示的关于[金属有机框架⊃导电聚合物]体系的结果总体上将作为一个原型实验，用于合理设计开发用于各种光电子应用的高导电性且具有荧光性的金属有机框架基材料。
