Crystal Structures and Redox Responses Coupled with Ion Recognition of p-Benzoquinone- and Hydroquinone-Fused [18]crown-6
Crystal Structures and Redox Responses Coupled with Ion Recognition of p-Benzoquinone- and Hydroquinone-Fused [18]crown-6
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对苯醌和氢醌稠合 [18]crown-6 的晶体结构和氧化还原响应与离子识别相结合
DOI：
10.1002/asia.201403262
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Tomoyuki Akutagawa
中科院分区：
文献类型：
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作者：
Takayuki Kobayashi;Yuta Nakane;Takashi Takeda;Norihisa Hoshino;Hidetoshi Kawai;Tomoyuki Akutagawa
研究了对苯二酚(BQ)稠合[18]冠-61和双BQ稠合[18]冠-62的晶体结构和氧化还原性能。这些BQ分子的阴离子自由基通过带负电荷的BQ部分和带正电荷的离子捕获单元[18]Crown-6之间的有效静电相互作用而稳定下来。静电相互作用和溶剂化能对决定还原电位中阳极氧化还原位移的大小起着重要作用。在晶体2中观察到规则的BQ单元的π堆积和规则的[18]冠-6单元阵列，其中一维π电子柱被离子通道分开。以单晶形式合成了对苯二酚稠合的[18]冠-6分子3和新的BQ和苯酚稠合的[18]冠-6衍生物4。[18]冠-6在晶体3和水合晶体3⋅H2O中的分子构象不同。
The crystal structures and redox properties ofp‐benzoquinone (BQ)‐fused [18]crown‐61and bis‐BQ‐fused [18]crown‐62were examined. The anion radicals of these BQ molecules were stabilized by addition of metal ions, through effective electrostatic interactions between the negatively charged BQ moiety and positively charged ion‐capturing [18]crown‐6 unit. The electrostatic interactions and solvation energy played important roles in determining the magnitudes of anodic redox shifts in the reduction potentials. Regular π‐stacking of BQ units and regular arrays of [18]crown‐6 units were observed in crystal2, in which one‐dimensional π‐electron columns were separated by ionic channels. The hydroquinone‐fused [18]crown‐6 molecule3and a new BQ‐ and phenol‐fused [18]crown‐6 derivative4were obtained as single crystals. The molecular conformations of [18]crown‐6 in crystal3and hydrated crystal3⋅H2O were different from each other.