Tayade Sakharam B, Dhavale Vishal M, Kumbhar Avinash S, Kurungot Sreekumar, Lönnecke Peter, Hey-Hawkins Evamarie, Pujari Bhalchandra
Department of Chemistry, Savitribai Phule Pune University, Pune- 411007, India.
Dalton Trans. 2017 May 30;46(21):6968-6974. doi: 10.1039/c7dt00425g.
Bipyridine glycoluril (BPG), a urea-fused bipyridine tecton, forms a square-pyramidal secondary building unit with copper(ii) which further self-assembles to give a porous hydrogen-bonded complex. This complex displays a high proton conductivity of 4.45 × 10 S cm at 90 °C and 95% relative humidity (RH). Chains consisting of coordinated water, solvent water and nitrate anions embedded in the complex are responsible for high proton conduction. The proton conduction pathway was corroborated by ab initio electronic structure calculations with molecular dynamics (MD) simulations using the Nudged Elastic Band (NEB) method. The theoretical activation energy estimated to be 0.18 eV is in close agreement with the experimental value of 0.15 eV which evidences a Grotthuss proton hopping mechanism. We thus demonstrate that the hydrogen-bonded complex encapsulating appropriate counter ions, coordinated water and solvent water molecules exhibts superprotonic conductivity.
联吡啶甘脲（BPG）是一种尿素稠合的联吡啶结构单元，它与铜（II）形成一个四方锥型二级建筑单元，该单元进一步自组装形成一种多孔氢键复合物。在90°C和95%相对湿度（RH）条件下，这种复合物显示出4.45×10 S cm的高质子传导率。嵌入复合物中的由配位水、溶剂水和硝酸根阴离子组成的链负责高质子传导。通过使用推挤弹性带（NEB）方法的分子动力学（MD）模拟进行的从头算电子结构计算，证实了质子传导途径。估计的理论活化能为0.18 eV，与0.15 eV的实验值非常吻合，这证明了Grotthuss质子跳跃机制。因此，我们证明了包裹适当抗衡离子、配位水和溶剂水分子的氢键复合物表现出超质子传导性。
