Exploration of new cooperative proton-electron transfer (PET) systems: first example of extended conjugated quinhydrones, 1,5-dihalo-2,6-naphthoquinhydrones
Exploration of new cooperative proton-electron transfer (PET) systems: first example of extended conjugated quinhydrones, 1,5-dihalo-2,6-naphthoquinhydrones
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新型合作质子电子转移（PET）系统的探索：扩展共轭氢醌，1,5-二卤-2,6-萘醌氢酮的第一个例子
DOI：
10.1021/ja00005a078
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发表时间：
1991
影响因子：
15
通讯作者：
I. Murata
中科院分区：
文献类型：
--
作者：
K. Nakasuji;K. Sugiura;T. Kitagawa;J. Toyoda;H. Okamoto;Kaoru Okaniwa;T. Mitani;H. Yamamoto;I. Murata
图3.CNQH的OH伸缩区的吸收光谱与压力的关系(左)，BQH和CNQH的CT跃迁能(右)深入研究互变异构体(···-N-HN)，例如在偶氮苯6和二苯并四氮[14]轮烯中。9固体状态下这些现象的一般特征是在初始状态和最终状态下闭合壳体结构之间的多个(在这些情况下，是双)模式的PETreaction。PET表示，可能存在的具有开壳结构的中间态的细节已经开始揭开。6我们特别关注的是通过利用固体中存在的氢键和CT之间的联合化学作用来稳定这种PET状态。原型是在物理手段诱导的压力下发现的BQH的相变。5考虑到反应是逐步进行的，我们可以在分子水平上可视化相变，如图1所示。因此，PET状态可能是由单个ET与单个PT(A-*B-*D)或单个PT与单个ET(A-*C-*D)相结合而产生的。寻求在较温和的物理条件下，特别是在环境条件下实现这样一种合作的PET状态，可以打开一种潜在的有趣的固态性质的新途径。忽略A和B(或C和D)态之间的量子力学混合或CT相互作用，以及A和C(或B和D)态之间的质子隧穿，最终的PET态(D)可以表征为H键中性自由基的分子组装。
Figure 3. Pressure dependence (left) of the absorption spectra in the OH stretching regions for CNQH and (right) of the CT transition energies for BQH and CNQH. intensive investigations on the tautomerism (···—N—HN), for example, in azophenine6 and dibenzotetraaza [14] annulene. 9 General features of these phenomena in the solid state are multiple (in these cases, double) modes of PETreactions between closed-shell structures in the initial and thefinal states. Details of the possible intermediate states with open-shell structures, the PET states, have begun to unravel. 6 Our particular attention is concentrated on stabilization of such a PET state by using the combined chemical interactions between H-bonding and CT present in the solid. The prototype is the phase transition found for BQH under pressure induced by physical means. 5 Considering the reaction as if it were stepwise, we can visualize the phase transition on a molecular level as shown in Figure 1. Thus, the PET state might be produced by single ET associated with single PT (A-* B-*D), or single PT associated with single ET (A-* C—* D). The search for the realization of such a cooperative PET state under milder physical conditions, ambient conditions in particular, can open a new approach to potentially interesting solid-state properties. Neglecting the quantum-mechanical mixing, or CT interaction between the A and B (or Cand D) states and proton tunneling between the A and C (or B and D) states, the final PETstate (D) can be characterized as a molecular assembly of H-bonded neutral radicals.