Protonic Conductivity and Hydrogen Bonds in (Haloanilinium)(H2PO4) Crystals
Protonic Conductivity and Hydrogen Bonds in (Haloanilinium)(H2PO4) Crystals
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(卤苯胺)(H2PO4) 晶体中的质子电导率和氢键
DOI：
10.1021/acs.jpcc.5b06665
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发表时间：
2015
影响因子：
3.7
通讯作者：
T.
中科院分区：
文献类型：
--
作者：
Yoshii;Y.; Hoshino;N.; Takeda;T.; Akutagawa;T.
磷酸（H_3PO_4）与卤代苯胺在醇中发生Br_nsted酸碱反应，生成1：1的（X-anilinium ~+）（H_2PO_4 ~-）和2：1的（X-anilinium ~+）_2（HPO_4 ~（2-））质子转移离子盐（X = F，Cl，Br和I，在苯胺的o，m和p位）。只有前者的1：1单晶在N2条件下表现出质子导电性，而后者的2：1单晶成为质子绝缘体。在晶体中，不同的氢键结构从一维到二维网络实现了通过修改的分子结构的X-苯胺阳离子。质子电导率与氢键网络中H2 PO 4-阴离子的连通性有关。邻氯苯胺（H_2PO_4 ~-）和邻溴苯胺（H_2PO_4 ~-）中的氢键梯状链导致了最高的质子电导率为10 ~（-3）S cm ~（-1）。梯形链（H_2PO_4 ~-）排列的质子电导率比二维片的高。通过对单晶X射线结构的差分傅立叶分析，分析了质子的运动自由度。二维层（包括（H2 PO 4-）2二聚体和（H2 PO 4-）4四聚体）显示出相对较低的质子导电性，并且通过增加H2 PO 4-阴离子之间的氢键连接性和均匀性来降低质子导电性的活化能。
Brønsted acid–base reactions between phosphoric acid (H3PO4) and haloanilines in alcohols formed 1:1 proton-transferred ionic salts of (X-anilinium+)(H2PO4–) and 2:1 ones of (X-anilinium+)2(HPO42–) (X = F, Cl, Br, and I at o, m, and p positions of anilinium). Only the former 1:1 single crystals showed proton conductivity under the N2condition, and the latter 2:1 crystals became protonic insulators. In crystals, diverse hydrogen-bonding structures from 1D to 2D networks were achieved by modification of the molecular structure of X-anilinium cations. The protonic conductivity was associated with the connectivity of H2PO4–anions in the hydrogen-bonding networks. The hydrogen-bonding ladder chains in (o-cloroanilinim)(H2PO4–) and (o-bromoanilinim)(H2PO4–) resulted in the highest protonic conductivity of ∼10–3S cm–1. The protonic conductivity of the ladder-chain (H2PO4–) arrangements was higher than that of 2D sheets. The motional freedom of protons was analyzed by difference Fourier analysis of the single-crystal X-ray structure. The 2D layer, including (H2PO4–)2dimers and (H2PO4–)4tetramers, showed relatively low protonic conductivity, and the activation energy for proton conductivity was lowered by increasing the hydrogen-bonding connectivity and uniformity between H2PO4–anions.