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Construction of Supramolecular Polymer Gels Cross-linked by Two Types of Discrete Well-defined Metallacycles through Self-sorting
增强出版- Acta Polymerica Sinica Issue 1, Pages: 71-79(2017)
- 作者机构：
华东师范大学化学与分子工程学院 上海 200062
- 作者简介：
- 基金信息：
DOI：10.11777/j.issn1000-3304.2017.16238
CLC：Published：2017-1，
Received：29 July 2016，
Revised：25 August 2016，
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Zhang Chang-wei, Ou Bo, Yin Guang-qiang, Chen Li-jun, Yang Hai-bo. Construction of Supramolecular Polymer Gels Cross-linked by Two Types of Discrete Well-defined Metallacycles through Self-sorting. [J]. Acta Polymerica Sinica (1):71-79(2017)
Zhang Chang-wei, Ou Bo, Yin Guang-qiang, Chen Li-jun, Yang Hai-bo. Construction of Supramolecular Polymer Gels Cross-linked by Two Types of Discrete Well-defined Metallacycles through Self-sorting. [J]. Acta Polymerica Sinica (1):71-79(2017) DOI： 10.11777/j.issn1000-3304.2017.16238.
摘要
通过合理分子设计，合成了分别含有柱芳烃主体基元和氰基客体基元且具有不同尺寸的吡啶给体
D1
和
D2
，同时选择120°双铂金属盐
A
作为受体，从三组分出发，通过“一锅法”配位键导向自组装，自分类得到分别含有3个柱[5]芳烃单元的金属有机大环
H
和含有3个氰基中性客体的金属有机大环G.随着体系浓度增大，通过柱芳烃共价大环与中性氰基客体之间主客相互作用，逐级自组装形成以2种分立金属有机大环为交联点的新型超分子聚合物.所得到的超分子聚合物通过变浓度核磁氢谱（
1
H-NMR）、动态光散射（DLS）、二维核磁扩散序谱（DOSY）、扫描电镜（SEM）等进行了表征.有趣的是，进一步增加浓度（9.9 wt%），超分子聚合物转化成超分子聚合物凝胶，并且在温度、中性有机小分子及卤素离子等多重刺激下实现凝胶-溶液的可逆转化.
Abstract
A dipyridyl donor
D1
decorated with pillar[5]arene unit and a dipyridyl donor
D2
containing neutral guest moiety were successfully synthesized. Through the X-ray single crystal analysis
it was found that the angle between the two pyridine unit in
D1
was about 128° and the distance between two nitrogen atoms was about 1.48 nm
while the angle between the two pyridine units of
D2
was about 118° and the distance between the two nitrogen atoms was about 0.98 nm
much shorter than that in
D1
. Thus
a metallacycle containing three pillar[5]arene units (
H
) and a metallacycle possessing three neutral guest units (
G
) were successfully constructed in one pot coordination-driven self-assembly from dipyridyl donors (
D1
and
D2
) and 120° di-Pt(II) acceptor through size-control self-sorting strategy. Moreover
driven by the host-guest interaction between metallacycles
H
and
G
a new family of supramolecular polymer
cross-linked by these two kinds of discrete well-defined metllacycles
H
and
G
was gradually constructed with the increase of concentration. By concentration-dependent
1
H-NMR measurement
it was found that the typical signals of metllacycle
G
were gradually disappeared with the increase of concentration
indicating the enhanced host-guest interaction between metallacycles
H
and
G
. Meanwhile
the analysis of 2-D diffusion ordered spectroscopy (DOSY) tests of
H
⊃
G
showed that the diffusion coefficient
D
gradually decreased with the increase of concentration
and
D
1 mmol/L
/
D
16 mmol/L
value was ca. 31.6
also demonstrating the formation of supramolecular polymer. Scanning electron microscope (SEM) was also used to investigate the morphology change during the concentration increasing process. More intuitionally
cross-linked networks were observed with the increase of concentration of
H
⊃
G
. Interestingly
the resultant supramolecular polymer could transforme into supramolecular polymer gels when the concentration was increased to a relatively high value (9.9 wt%). Moreover
due to the existence of discrete well-defined metallacycles and the dynamic nature of host-guest hierarchical self-assembly
reversible gel-sol transitions were successfully realized through the disassembly and reassembly of such cross-linked supramolecular polymer networks stimulated by various external stimuli such as temperature
competitive guest
and halide
etc
.
关键词
超分子聚合物凝胶配位键导向自组装主客体作用自分类
Keywords
Supramolecular polymer gelCoordination-driven self-assemblyHost-guest interactionSelf-sorting
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