面性不斉[2.2]パラシクロファンからなる光学活性
多孔性共役系高分子の合成
著者
梶原 正遥
[2.2] [ ] [2.2] (paracyclophane : PCP) PCP ( 3 ) PCP 1) PCP PCP 2)
(metal organic framework :
MOF)3) (covalent organic framework : COF)4)
(conjugated microporous polymer : CMP)
CMP MOF π 5) PCP 6) PCP PCP CMPs CMPs [ ] 7) (R p)-1
Pd2(dba)3 (dba = dibenzylideneacetone), PPh3, CuI
(Rp)-T1-monomer 48%
(Sp)-T1-monomer 49% rac-T1-monomer
47% (Rp)-1
2--5- (Rp)-T2-monomer 40% (Sp)-T2-monomer
43% rac-T2-monomer 54% (Rp
)-T1-monomer Ni(cod)2 (cod = cyclooctadiene), 2,2’-bipyridine
2019年度 修士論文要旨
関西学院大学大学院理工学研究科 環境・応用化学専攻 森崎研究室 梶原 正遥
(Rp)-T1-CMP 78% (Sp )-T1-CMP 86% rac-T1-CMP 115% (Rp)-T2-monomer (Rp)-T2-CMP 60% (Sp)-T2-CMP 25% rac-T2-CMP 99% T1-monomer |glum| = 0.6 × 10-3 T2-monomer |glum| = 0.9 × 10-3 T1-CMP |glum| = 0.6 × 10-3 T1-CMP 800 m2g-1
Scheme 1. Synthesis of target CMPs
1) Y. Morisaki, Y. Chujo, In π-Stacked Polymers and Molecules, Springer, Berlin, 2014, Chapter 3, pp 151-184. 2) Y. Morisaki, et al. Polym. Chem. 2012, 3, 2727 3) S. Kitagawa, et al. Angew.Chem.
Int. Ed. 2004, 43, 2334. 4) O. M. Yaghi, et al. Science 2017, 355, eaal1585. 5) A. I. Cooper Adv. Mater. 2009, 21, 1291. 6) Y. Morisaki, et al. J. Polym. Sci. Part A: Polym. Chem. 2013, 51(10),
2311. 7) Y. Morisaki, et al. J. Am. Chem. Soc. 2014, 136, 3350.
Br Br Br Br N N N N Br Br Br Br 1 T1-monomer T2-monomer T1-CMP λabs, max = 353 nm λPL, max = 420 nm Φlum = 31% |glum| = 0.9 × 10-3 λabs, max = 355 nm λPL, max = 418 nm Φlum = 44% |glum| = 0.6 × 10-3 λPL, max = 555 nm Φlum = 2% |glum| = 0.6 × 10-3 N N N N N N N N N N N N N NN N N N N N N N N N λPL, max = 418 nm Φlum = 20% T2-CMP
