SYNTHESIS AND PROPERTIES OF CHALCOGEN‐BRIDGED NAPHTHALENES: A NEW SERIES OF ELECTRON DONORS *
SYNTHESIS AND PROPERTIES OF CHALCOGEN‐BRIDGED NAPHTHALENES: A NEW SERIES OF ELECTRON DONORS *
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硫桥萘的合成和性质：一系列新的电子给体*
DOI：
10.1111/j.1749-6632.1978.tb39433.x
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发表时间：
1978
影响因子：
5.2
通讯作者：
Jon Clardy
中科院分区：
文献类型：
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作者：
D. Dauplaise;J. Meinwald;J. C. Scott;H. Temkin;Jon Clardy
有机电荷转移盐最近引起了人们的兴趣，在很大程度上，是由于在一类新的固体中实现高电导率的可能性。到目前为止，研究最多的开壳层阴、阳离子自由基分别是四氰基乙烯~-~（TCNE）、四氰基喹二甲烷~~*~-~（TCNQ）和四氰基萘喹二甲烷~*~*~-~（TNAP）及其衍生物，以及四硫富瓦烯（TTF）、1*2四硒富瓦烯（TSeF）家族的成员。制备这种配合物的一个主要问题是，在大多数情况下，物理性质无法预测。提出了各种分子标准，如小尺寸、高极化率、对称性和垂直于分子平面的分子轨道是获得金属导电性所必需的。然而，无法预先确定的特性（例如，晶体结构和分子间原子相互作用）也起着至关重要的作用。6在迄今为止制备的电荷转移复合物的大多数示例中，感兴趣的分子特性是不可预测的。这个问题的部分原因在于，数据一直缺乏一个大家庭的密切相关的化学结构。13为了解决其中的一些困难，我们已经进行了一类新的捐助者的研究：周桥萘二硫属化物（NDC的）。这些化合物在其结构中包含含有七个离域电子的平面稠合杂环，并且预期具有低电离电位，并且在电荷转移复合物中用作电子供体。待描述的第一个NDC是萘并[1，8-cd]-1，2-二硫杂环戊烯（I），其中二硫键桥连萘的邻位。“^'^Zweig和Hoffmannl'表明I是一个很好的电子供体，其半波氧化电位（0.95 V vs. s.）就证明了这一点。C. e.）以及其与受体如四氯苯醌和TCNE形成电荷转移络合物的能力。直到最近我还是唯一一个...
The recent interest in organic charge-transfer salts has been aroused, to a large extent, by the possibility of achieving high conductivity in a novel class of solids.'*' To date, the most widely studied open-shell anion and cation radicals have been tetra~yanoethylene~-~ (TCNE), tetracyanoquin~dimethane~~~*~-~ (TCNQ) and tetracyanonaphthoquin~dirnethane~*~*~~'~ (TNAP) and their derivatives, and members of the tetrathiafulvalene (TTF)1*2 tetraselenaf~lvalene"*~' (TSeF) families respectively. A major problem in the preparation of such complexes is that the physical properties cannot, for the most part, be predicted. It has been suggested that various molecular criteria, such as small size, high polarizability, symmetry, and molecular orbitals perpendicular to the plane of the molecule are necessary to achieve metallic cond~ctivity.~ However, characteristics that cannot be predetermined-for example, crystal structure and intermolecular atomic interactions-also play a crucial role.6 In most examples of charge-transfer complexes prepared to date, the molecular properties of interest have not been predictable. Part of this problem lies in the fact that data have been lacking on a large family of closely related chemical structures.13 In order to address some of these difficulties, we have undertaken the study of a new class of donors: peri-bridged naphthalene dichalcogenides (NDC's). These compounds incorporate within their structure a planar-fused heterocyclic ring containing seven delocalizable electrons, and are expected to have low ionization potentials and to function as electron donors in charge-transfer c~mplexes . ' ~ '~ The first NDC to be described was naphtho[l,8-cd]-l,2-dithiole (I), in which a disulfide linkage bridges naphthalene's peri position^."^'^ Zweig and Hoffmannl' showed that I is a good electron donor, as evidenced by its half-wave oxidation potential (0.95 V vs. s. c. e.) and its ability to form charge-transfer complexes with acceptors such as chloranil and TCNE. Until recently, I was the only known mem-
T. Takeichi.：“金属苯甲酰丙酮酸盐和乙酰丙酮与甲醛的反应”Bull。
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