Synthesis of Non-Kekule Type π-Conjugated Polymers and Co-operative Multiple-Spin Alignment

非凯库勒型π共轭聚合物的合成及协同多自旋排列

• 批准号: 09305060
• 负责人: NISHIDE Hiroyuki
• 金额: $ 20.29万
• 依托单位: Waseda University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09305060/
• 关键词: Conjugated Polymer; Precision Polymerization; Polycondensation; Polyradical; High-Spin Polymer; Magnetic Polymer

Objectives of this research are the synthesis of π-conjugated polymers bearing pendant radical groups on every monomer unit, which are substituted on the polymer backbone to satisfy a π-conjugated but non-Kelule structure, and the study on strong and through-bond ferromagnetic exchange interaction between and alignment of the multiple spins of the pendant radicals.(1) Bromostyrene dirivatives were polycondensated with a Pd-phosphine catalyst to yield π-conjugated star-shaped or hyperbranched poly (4-phenoxyl-1, 2-phenylenevinylene) s. SQUID and pulsed ESR measurements revealed the spin-alignment, e. g., with S = 10/2.(2) Linear, acyclic, and cyclic poly (phenoxy-phenyleneethynylene) s were synthesized by the polycondensation of the iodostyrene derivatives with a Pd/Cu catalyst. The cyclic and conjugated one was an effective spin pathway.(3) Diphenylaminium cation radical was introduced as a spin source to poly (4-substituted 1, 2-phenylenevinylene) to realize both a sufficient ferromagnetic interaction and chemical stability even at room temperature. Stability of the multiplet ground state was significantly large to first give a highspin and durable organic polymer.

这项研究的目的是在每个单体单元上携带垂直激进基团的π共偶联的聚合物的合成，这些单体都在聚合物骨架上进行，以满足π偶联但非kelule结构的研究，以及对强和整个键的铁磁体交流和对1.1 s radicer of porders of sorders of sorders of sorders of sorders of sorders rad radys rad radys rad rad radicer of sorders rad radicer sorders of sorders of sorders rad radicer（1）的研究。用PD-磷酸催化剂聚合降低，以产生π偶联的星形或超支的聚（4-苯氧基-1，2-苯基乙烯基）s。鱿鱼和脉冲的ESR测量结果揭示了自旋对齐，e。 g。，s = 10/2。（2）线性，无环和环状聚（苯氧基 - 苯基乙烯烯）S通过用Pd/cu催化剂的碘斯坦烯衍生物的多敏合成。循环和共轭是有效的自旋途径。（3）将二苯基氨基阳离子自由基作为旋转源，作为聚（4-取代的1、2-苯乙烯）的自旋源，以实现足够的铁磁相互作用和化学稳定性，即使在室温下也是如此。多重基态的稳定性明显很大，首先给出高螺旋和耐用的有机聚合物。

项目成果

H.Nishide, M.Takahashi et al.: "High-Spin Oxyphenylbenzo-Annelated Dehydro[12]annulene"Chem. Lett.. 1999. 161-162 (1999)

H.Nishide、M.Takahashi 等人：“高自旋氧苯基苯并稠合的脱氢[12]轮烯”Chem。

T. Michinobu, M. Takahashi, E. Tsuchida and H. Nishide: "Robust Triplet Molecule : Cationic Diradical of 3, 4'-Bis (diphenylamino) stilbene"Chem. Mater.. 11. 1969-1971 (1999)

T. Michinobu、M. Takahashi、E. Tsuchida 和 H. Nishide：“稳健的三重态分子：3, 4-双（二苯氨基）芪的阳离子双自由基”Chem。

M.Takahashi, H.Nishide et al.: "Nonlinear Optical Property of Poly(phenylenevinylene) Bearing π-Conjugated Radicals"Mol. Cryst.Liq. Cryst.. 334. 31-39 (1999)

M.Takahashi、H.Nishide 等：“带有 π-共轭自由基的聚(亚苯基亚乙烯基) 的非线性光学性质”Cryst.Liq. 334. 31-39 (1999)

H. Nishide, M. Miyasaka and E. Tsuchida: "High-Spin Polyphenoxyls Attached to Star-Shaped Poly (phenylenevinylene) s"J. Org. Chem.. 63. 7399-7407 (1998)

H. Nishide、M. Miyasaka 和 E. Tsuchida：“连接到星形聚（亚苯基亚乙烯基）的高自旋聚苯氧基”J。

H. Nishide, M. Takahashi et al.: "Optical nonlinearity of an open-shell and degenerate π-conjugated polymer : poly (4-oxyphenyl-1,2-phenylenevinylene) radical" Chem. Commun.1997. 1853-1854 (1997)

H. Nishide、M. Takahashi 等人：“开壳层简并 π 共轭聚合物的光学非线性：聚（4-氧苯基-1,2-亚苯基亚乙烯基）自由基”Chem.1997。 1997)