Aromaticity gain increases the inherent association strengths of multipoint hydrogen-bonded arrays
Aromaticity gain increases the inherent association strengths of multipoint hydrogen-bonded arrays
复制标题
芳香度增益增加了多点氢键阵列的固有缔合强度
DOI：
10.1039/c8cc00422f
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发表时间：
2018
影响因子：
4.9
通讯作者：
Wu, Judy I.
中科院分区：
文献类型：
--
作者：
Wu, Chia-Hua;Zhang, Yu;van Rickley, Krista;Wu, Judy I.
长期以来，教科书对多点氢键阵列关联的解释一直依赖于二次静电相互作用（SEI）模型，这表明阵列关联强度取决于相互作用单元的质子供体(D)和受体(A)模式。这里，基于块局域波函数（BLW）方法的计算结果揭示了SEI模型的局限性，相反，在气相（和隐式氯仿溶剂化）中，多点氢键阵列的固有自由能与络合后阵列的“芳香性增益”程度（即循环π-电子离域增加的量）相关。46个三层（r = 0.940）和四层（r = 0.959）氢键阵列具有良好的相关性。
Textbook explanations for the associations of multipoint hydrogen-bonded arrays have long hinged on the secondary electrostatic interaction (SEI) model, which suggests that array association strengths depend on the proton donor (D) and acceptor (A) patterns of the interacting units. Here, computational results based on the block-localized wavefunction (BLW) method reveal limitations of the SEI model, demonstrating instead that, in the gas-phase (and in implicit chloroform solvation), the inherent free-energies of associations of multipoint hydrogen-bonded arrays correlate with the degree of “aromaticity gain” (i.e., the amount of increased cyclic π-electron delocalization) in arrays upon complexation. Excellent correlations for 46 triply (r = 0.940) and quadruply (r = 0.959) hydrogen-bonded arrays are presented.