Nature of the E---E' interactions (E, E' = O, S, Se, and Te) at naphthalene 1,8-positions with fine details of the structures: experimental and theoretical investigations
Nature of the E---E' interactions (E, E' = O, S, Se, and Te) at naphthalene 1,8-positions with fine details of the structures: experimental and theoretical investigations
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萘 1,8 位 E---E 相互作用（E、E = O、S、Se 和 Te）的性质以及结构的详细信息：实验和理论研究
DOI：
10.1039/c9nj02198a
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发表时间：
2019
期刊：
影响因子：
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通讯作者：
Norihiro Tokitoh and Mao Minoura
中科院分区：
文献类型：
--
作者：
Satoko Hayashi;Manabu Uegaito;Taro Nishide;Eiichiro Tanaka;Waro Nakanishi;Takahiro Sasamori;Norihiro Tokitoh and Mao Minoura
在对 1-(PhE)–8-(PhE′)C10H6 (3a-3f) 进行结构测定后，用 QTAIM-DFA 阐明了 1-(MeE)–8-(MeE′)C10H6 [1a–1f (E ≠ E′) 和 1g–1j (E = E′)] 1,8 位上 E⋯E′ 相互作用的内在动态和静态性质，其中(E, E′: x) = (O, S: a), (O, Se: b), (O, Te: c), (S, Se: d), (S, Te: e), (Se, Te: f), (O, O: g), (S, S: h), (Se, Se: i) 和 (Te, Te: j) (χE ≥ χE′)。虽然 3a、3b 和 3d–3f 的 AB 结构被确认，由 np(E)⋯σ*(E'–CPh) 相互作用组成，但 3c 的结构是 BB，其中 E–CR/E'–CR (R = Ph) 键垂直于 A 中的萘基平面，并且位于 B 的平面上。虽然 AB 结构由 p(E)–π(Ph) 共轭决定，但 BB 结构是通过晶体堆积效应。未检测到具有 np(E′)⋯σ*(E–CPh) 的 BA 结构。 BB、AA 和 BA 具有典型的共价氢键性质，预测了 1e 和 1f 中 AB 的 CT-MC（通过电荷转移形成分子复合物）性质（对于 E-CR/E'-CR，R = Me），而 1j 的所有构象异构体的 CT-MC 性质均被预测。对1a-1f的NBO分析表明，受主轨道的贡献远大于供主轨道，其顺序为 σ*(O–CMe: <0.5 kcal mol−1) ≪ σ*(S–CMe: ≈5 kcal mol−1) ≪ σ*(Se–CMe: ≈10 kcal mol−1) ≪ σ*(Te–CMe: ≈16 kcal mol−1) 对于 np(S)、np(Se) 和 np(Te)。如果分别分析 σ*(S–C)、σ*(Se–C) 和 σ*(Te–C)，则 E(2) 值与 1a–1j 的 AB 和/或 BA 的 Cii−1 成比例相关。
The intrinsic dynamic and static natures of the E⋯E′ interactions at the 1,8-positions of 1-(MeE)–8-(MeE′)C10H6 [1a–1f (E ≠ E′) and 1g–1j (E = E′)] were elucidated with QTAIM-DFA, after structural determination of 1-(PhE)–8-(PhE′)C10H6 (3a–3f), where (E, E′: x) = (O, S: a), (O, Se: b), (O, Te: c), (S, Se: d), (S, Te: e), (Se, Te: f), (O, O: g), (S, S: h), (Se, Se: i) and (Te, Te: j) (χE ≥ χE′). While the AB structures are confirmed for 3a, 3b and 3d–3f, which consist of the np(E)⋯σ*(E′–CPh) interactions, the structure was BB for 3c, where the E–CR/E′–CR (R = Ph) bond is perpendicular to the naphthyl plane in A and it is placed on the plane in B. While the AB structures are determined by the p(E)–π(Ph) conjugations, the BB structure is by the crystal packing effect. The BA structure with np(E′)⋯σ*(E–CPh) was not detected. While the nature of a typical hydrogen bond with covalency was predicted for BB, AA and BA, with the CT-MC (molecular complex formation through charge transfer) nature for AB in 1e and 1f (R = Me for E–CR/E′–CR), the CT-MC nature was predicted for all conformers of 1j, for example. NBO analysis for 1a–1f revealed that the acceptor orbitals contribute much more than the donor orbitals and the order is σ*(O–CMe: <0.5 kcal mol−1) ≪ σ*(S–CMe: ≈5 kcal mol−1) ≪ σ*(Se–CMe: ≈10 kcal mol−1) ≪ σ*(Te–CMe: ≈16 kcal mol−1) for np(S), np(Se) and np(Te). The E(2) values proportionally correlate to Cii−1 for AB and/or BA of 1a–1j, if analyzed separately for σ*(S–C), σ*(Se–C) and σ*(Te–C).