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.

本研究的目的是合成每个单体单元上都有悬垂自由基基团的π共轭聚合物，并将其取代在聚合物主链上以满足π共轭但非kelule结构，并研究悬垂自由基的多个自旋之间的强铁磁交换、相互作用和排列。(1)溴苯乙烯衍生物在pd -膦催化剂下缩聚得到π共轭星形或超支化聚（4-苯氧基- 1,2 -苯乙烯）s。SQUID和脉冲ESR测量显示自旋取向为s = 10/2。(2)在Pd/Cu催化剂的催化下，通过缩聚反应合成了线性、无环和环状聚苯氧基苯乙烯。环状共轭自旋途径是一种有效的自旋途径。(3)将二苯胺阳离子自由基作为自旋源引入聚（4-取代1,2 -苯基乙烯）中，使其在室温下具有足够的铁磁相互作用和化学稳定性。多重基态的稳定性显著提高，首次获得了高自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: "Average Octet Radical Polymer : A Stable Polyphenoxyl with Star-Shaped π-Conjugated"Angew. Chem. Int. Ed.. 37. 2400-2402 (1998)

H. Nishide、M. Miyasaka 和 E. Tsuchida：“平均八位基自由基聚合物：具有星形 π 共轭的稳定聚苯氧基”Angew Int. Ed. 37. 2400-2402 (1998)

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。