Meng Zheng, Stolz Robert M, Mirica Katherine A
Department of Chemistry, Burke Laboratory , Dartmouth College , Hanover , New Hampshire 03755 , United States.
J Am Chem Soc. 2019 Jul 31;141(30):11929-11937. doi: 10.1021/jacs.9b03441. Epub 2019 Jul 17.
This paper describes the synthesis of a novel intrinsically conductive two-dimensional (2D) covalent organic framework (COF) through the aromatic annulation of 2,3,9,10,16,17,23,24-octa-aminophthalocyanine nickel(II) and pyrene-4,5,9,10-tetraone. The intrinsic bulk conductivity of the COF material (termed ) reached 2.51 × 10 S/m, and increased by 3 orders of magnitude with I doping. Electronic calculations revealed an anisotropic band structure, with the possibility for significant contribution from out-of-plane charge-transport to the intrinsic bulk conductivity. Upon integration into chemiresistive devices, this conductive COF showed excellent responses to various reducing and oxidizing gases, including NH, HS, NO, and NO, with parts-per-billion (ppb) limits of detection (for NH = 70 ppb, for HS = 204 ppb, for NO = 5 ppb, and for NO = 16 ppb based on 1.5 min exposure). Electron paramagnetic resonance spectroscopy and X-ray photoelectron spectroscopy studies suggested that the chemiresistive response of the involves charge transfer interactions between the analyte and nickelphthalocyanine component of the framework.
本文描述了通过2,3,9,10,16,17,23,24-八氨基酞菁镍(II)与芘-4,5,9,10-四酮的芳香环化反应合成一种新型本征导电二维(2D)共价有机框架(COF)。该COF材料（称为 ）的本征体电导率达到2.51×10 S/m，并且通过碘掺杂电导率提高了3个数量级。电子计算揭示了一种各向异性的能带结构，其中面外电荷传输对本征体电导率有显著贡献。将这种导电COF集成到化学电阻器件中后，它对包括NH₃、H₂S、NO₂和NO在内的各种还原性和氧化性气体表现出优异的响应，检测限可达十亿分之一(ppb)（基于1.5分钟暴露时间，对于NH₃ = 70 ppb，对于H₂S = 204 ppb，对于NO₂ = 5 ppb，对于NO = 16 ppb）。电子顺磁共振光谱和X射线光电子能谱研究表明，该 的化学电阻响应涉及分析物与框架中镍酞菁组分之间的电荷转移相互作用。
