Ambidextrous circular dichroism and circularly polarised luminescence from poly(9,9-di-n-decylfluorene) by terpene chirality transfer
Ambidextrous circular dichroism and circularly polarised luminescence from poly(9,9-di-n-decylfluorene) by terpene chirality transfer
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DOI：
10.1039/b9py00288j
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发表时间：
2010-06-01
影响因子：
4.6
通讯作者：
Fujiki, Michiya
中科院分区：
文献类型：
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作者：
Nakano, Yoko;Liu, Yang;Fujiki, Michiya
利用柠檬烯和α-蒎烯的对映体进行溶剂手性转移，成功制备了具有圆二色性（CD）和圆偏振发光（CPL）特性的光学活性聚（9，9-二正癸基芴）（PF 10）聚集体。在25 ℃下，借助于溶剂手性转移，通过CD-/CPL-沉默PF 10快速产生聚集体。我们证明：（i）通过弱力，如pi/pi、货车德瓦尔斯和CH/pi相互作用，CD-/CPL-活性PF 10聚集体成功地出现在氯仿的手性互溶体系中（作为良溶剂），烷醇（作为不良溶剂）和萜烯（作为手性溶剂），（ii）PF 10的分子量，PF的烷基链长度，萜烯结构和对映体纯度，溶剂类型，和溶液温度极大地影响CD-/CPL-信号的幅度和符号，（iii）涡旋和聚集体尺寸仅轻微地影响这些信号的幅度，和（iv）来自PF 10聚集体的434 nm处的新CPL带，其由428 nm处的CD/UV-可见带产生，可能由手性β-相产生。本文证明的萜烯手性转移可以提供一种新的环境友好的、更安全的和更温和的方法，以在环境温度下从CD-/CPL-沉默聚合物快速生产双极性手性聚合物材料，而无需任何特定的手性催化剂或取代基。
Solvent chirality transfer using enantiomeric pairs of limonene and a-pinene allowed for the successful production of optically active poly(9,9-di-n-decylfluorene) (PF10) aggregates with circular dichroism (CD) and circularly polarised luminescence (CPL) properties. The aggregates were rapidly produced by CD-/CPL-silent PF10 with the aid of solvent chirality transfer at 25 degrees C. We demonstrate that: (i) through weak forces, such as pi/pi, van der Waals, and CH/pi interactions, CD-/CPL-active PF10 aggregates successfully emerge in a chiral tersolvent system of chloroform (as a good solvent), alkanol (as a poor solvent), and terpenes (as a chiral solvent), (ii) the molecular weight of PF10, alkyl chain length of PFs, terpene structure and enantiopurity, solvent type, and solution temperature greatly affect the magnitude and sign of the CD-/CPL-signals, (iii) the vortex and aggregate size only mildly affect the magnitude of these signals, and (iv) a new CPL band at 434 nm from PF10 aggregates, arising from the CD/UV-vis band at 428 nm, may result from a chiral beta-phase. The terpene chirality transfer demonstrated herein may provide a new environmentally friendly, safer, and milder process to rapidly produce ambidextrous chiroptical polymeric materials at ambient temperature from CD-/CPL-silent polymers without any specific chiral catalysts or substituents.