Syntheses and Electronic Properties of the Nickel and Palladium Complexes of the Octaethylporphyrin(M1)-(Dihexylbithiophene)_n-Octaethylporphyrin(M2) System [OEP(M1)-(DHBTh)_n-OEP(M2)] Connected with the Diacetylene Linkage. A Methodology for Molecular De

联乙炔键连接的八乙基卟啉(M1)-(二己基联噻吩)_n-八乙基卟啉(M2)体系[OEP(M1)-(DHBTh)_n-OEP(M2)]的镍和钯配合物的合成和电子性质。

• 批准号: 14540489
• 负责人: HIGUCHI Hiroyuki
• 金额: $ 1.86万
• 依托单位: Faculty of Science, Toyama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540489/
• 关键词: dihexylbithiophene; octaethylporphyrin; diacetylene; coupling; energy transfer; electron transfer; extended conjugation system; orientational isomers

The synthetic methods for both symmetrical and unsymmetrical complexes of the OEP(M)-DHBTh-OEP(M) system have been conclusively described. Particularly, it is notable that the synthetic success of the terminal acetylenes 42 and 51 would lead to a general synthetic method for a variety of the OEP(M)-DHBTh-(π-EC) derivatives and would impel the present research onto the further application stage. ^1H NMR spectral study makes it confirmed that all the OEP(M)-(DHBTh)_n-OEP(M) derivatives possess the fairly simple skeletal features, regardless of the symmetry of molecule, with the respective ring currents of OEP(M) in 36 and 37 remaining to a great extent. And thus, the deshielded area from anisotropic effect of OEP(M) has proven to expand up to 25Å for the Ni complexes and 30Åfor the Pd complexes, reflecting the magnitudes of their ring currents (Fig.3). From the IR spectral measurements, it is derived that the diacetylene linkage for the TT series exhibits a greater contribution to an ext … More ension of the resonance structure with the OEP and DHBTh nuclei, regardless of the number of DHBTh. As contrasted with such a simple regularity in a rigid and straight molecular skeleton, the present π-electronic conjugation system possess characteristic absorption spectral features, reflecting several structure elements. The appearances of Soret and Q bands are peculiar to the present one-dimensionally extended π-electronic conjugation system, which exactly reflect the orientation of DHBTh. Absorption spectra for the HH,HT and TT isomers 1-3 show the respective Soret bands to split into two mainπ→π* transitions regularly, among which all the shorter wavelength λ_1 bands appear at around 440nm. The longer wavelength λ_2 bands, however, appear at the longer wavelength region separately over a range of 45nm. In both HH and TT series, the spectra of the Pd complexes 4 and 5 exhibit slight hypsochromic shift and sharpened, as compared with those for the corresponding Ni complexes 1 and 3. It is also proved that the introduction of (DHBTh)_n into 36 and 37 to form OEP(M)-(DHBTh)_n-OEP(M) (8-25) induces the gradual reformation between the two main electronic structures, reflecting both the orientation and n of DHBTh. With increases of n, the HH series the combined electronic system between OEP(M)-HTh and HTh-HH(DHBTh)_<n-2>-HTh, while the TT series does the conjugation system between OEP(M)-TT(DHBTh) and TT(DHBTh) _<n-2> (Fig.10). The solvent-dependent spectra of the OEP(Ni)-TT(DHBTh)-OEP(Pd) derivative 7 have been remarkably observed, though the transition origins of the sensitive bands to the solvent polarity must be further clarified. Concurrently with the orientation of DHBTh, the unsymmetrization by introducing the different OEP(M) rings into the present system is also potentially effective to conduct the electron transfer functionality from one side to the other.In consequence, the electronic absorption spectra of the OEP(M1)-(DHBTh)_n-OEP(M2) system could be affected substantially by the following structure elements. Putting those structure elements together from the material viewpoint, the orientation of DHBTh could be regarded as a function selector to construct the main electronic structure of the system, the incorporated metal ions M as a modulation tool for adjustment of the transition energy for each function band and the number of DHBTh as a fine tuner to select the susceptibility to the external electronic stimulations. Therefore, a particular electronic structure of OEP(M1)-(DHBTh)_n-OEP(M2) corresponding to the particular electronic property would be constructed by choosing these three structure elements purposively. Since the structure elements could be generalized to expand into the orientations of DABTh, many other metal ions and the greater numbers of n, respectively, the present study would provide a methodology for construction of the particular electronic structures of various DABTh derivatives at the stage of molecular design. Less

总结性地描述了 OEP(M)-DHBTh-OEP(M) 系统对称和不对称配合物的合成方法。特别值得注意的是，末端乙炔42和51的合成成功将导致多种OEP(M)-DHBTh-(π-EC)衍生物的通用合成方法，并将推动目前的研究进入进一步的应用阶段。 ^1H NMR谱研究证实，无论分子的对称性如何，所有OEP(M)-(DHBTh)_n-OEP(M)衍生物都具有相当简单的骨架特征，OEP(M)在36和37中各自的环电流在很大程度上保留。因此，OEP(M)各向异性效应的去屏蔽区域已被证明对于Ni配合物扩大了25Å，对于Pd配合物扩大了30Å，反映了它们环电流的大小（图3）。根据红外光谱测量，得出 TT 系列的丁二炔键对 OEP 和 DHBTh 核的共振结构的外延贡献更大，无论 DHBTh 的数量如何。与刚性且直的分子骨架中这种简单的规律性相比，当前的π电子共轭体系具有特征吸收光谱特征，反映了多种结构元素。 Soret和Q带的出现是目前一维扩展的π电子共轭体系特有的，它准确地反映了DHBTh的取向。 HH、HT和TT异构体1-3的吸收光谱显示各自的Soret带有规律地分裂成两个主要的π→π*跃迁，其中所有较短波长的λ_1带出现在440nm附近。然而，较长波长λ_2波段分别出现在45nm范围内的较长波长区域。在 HH 和 TT 系列中，与相应的 Ni 配合物 1 和 3 相比，Pd 配合物 4 和 5 的光谱表现出轻微的深色偏移和锐化。还证明，将 (DHBTh)_n 引入到 36 和 37 中形成 OEP(M)-(DHBTh)_n-OEP(M) (8-25) 会引起两个主要电子之间的逐渐重整。 结构，反映 DHBTh 的方向和 n。随着n的增加，HH系列是OEP(M)-HTh和HTh-HH(DHBTh)_<n-2>-HTh之间的组合电子系统，而TT系列是OEP(M)-TT(DHBTh)和TT(DHBTh)_<n-2>之间的共轭系统(图10)。 OEP(Ni)-TT(DHBTh)-OEP(Pd)衍生物7的溶剂依赖性光谱已被显着观察到，但敏感带对溶剂极性的跃迁起源还需要进一步阐明。与 DHBTh 的取向同时，通过在本系统中引入不同的 OEP(M) 环来实现不对称化也可能有效地将电子转移功能从一侧传导到另一侧。因此，OEP(M1)-(DHBTh)_n-OEP(M2) 系统的电子吸收光谱可能会受到以下结构元素的显着影响。从材料的角度将这些结构元素放在一起，DHBTh的方向可以被视为构建系统主要电子结构的功能选择器，掺入的金属离子M可以作为调节工具，用于调整每个功能带的跃迁能量，而DHBTh的数量可以作为微调器，以选择对外部电子刺激的敏感性。因此，通过有目的地选择这三个结构元素，可以构造出与特定电子性质相对应的特定电子结构OEP(M1)-(DHBTh)_n-OEP(M2)。由于结构元素可以推广到分别扩展到 DABTh、许多其他金属离子和更大数量的 n 的方向，因此本研究将为在分子设计阶段构建各种 DABTh 衍生物的特定电子结构提供一种方法。较少的

项目成果

Naoto Hayahsi: "Electronic Properties of the Nickel and Palladium Complexes of the Octaethylporphyrin(M)-(Dihexyl-bithiophene)n-Octaethylporphyrin(M) [OEP(M)-(DHBTh)n-OEP(M)] System Connected with Diacetylene Linkage. A Methodology for Molecular Design of

Naoto Hayahsi：“与丁二炔相连的八乙基卟啉(M)-(二己基联噻吩)n-八乙基卟啉(M) [OEP(M)-(DHBTh)n-OEP(M)]体系的镍和钯配合物的电子性质

Naoto Hayashi: "Synthesis and Properties of Unsymmetrically Extended π-Electronic Conjugation System of Octaethylporphyrin(Ni)-Dihexylbithiophene-Octaethylporphyrin(Pd) Connected with Diacetylene Linkage"Tetrahedron Lett.. 44. 7155-7158 (2003)

Naoto Hayashi：“与二乙炔键连接的八乙基卟啉（Ni）-二己基联噻吩-八乙基卟啉（Pd）的不对称扩展π电子共轭体系的合成和性质”Tetrahedron Lett.. 44. 7155-7158 (2003)

K.Tani: "Synthesis and photophysical properties of [m.n]carbazolophanes in the chemistry book (Chapter 9) ; Cyclophane Chemistry for 21st Century"ed. by H.Takemura, Transworld Research Network (India)(印刷中). (2003)

K.Tani：“化学书中[m.n]咔唑啉的合成和光物理性质（第 9 章）；21 世纪环芳化学”，H.Takemura 编，Transworld Research Network（印度）（2003 年出版）。

Hayashi N., Matsuda A., Chikamatsu M., Mori K., Higuchi H.: "Synthesis and Properties of Unsymmetrically Extended π-Electronic Conjugation System of Octaethylporphyrin(Ni)-Dihexylbithiophene-Octaethylporphyrin(Pd) Connected with Diacetylene Linkage"Tetrah

Hayashi N.、Matsuda A.、Chikamatsu M.、Mori K.、Higuchi H.：“二乙炔键连接的八乙基卟啉（Ni）-二己基联噻吩-八乙基卟啉（Pd）的不对称扩展π电子共轭体系的合成和性质”Tetrah

Tani K., Matsumura K., Togo E., Hori K., Tohda Y., Takemura H., Ohkita H., Ito S., Yamamoto M.: "Synthesis and Properties of Carbazole-Terephthalate Cyclophane"Chemistry Lett.. 910-911 (2003)

Tani K.、Matsumura K.、Togo E.、Hori K.、Tohda Y.、Takemura H.、Ohkita H.、Ito S.、Yamamoto M.：“咔唑对苯二甲酸酯环烷的合成和性能”Chemistry Lett..