The investigation of the hydrogen bond saturation effect during the dipole-dipole induced azobenzene supramolecular self-assembly
The investigation of the hydrogen bond saturation effect during the dipole-dipole induced azobenzene supramolecular self-assembly
复制标题
偶极-偶极诱导偶氮苯超分子自组装过程中氢键饱和效应的研究
DOI：
10.1039/c3cp52864b
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发表时间：
2013-01-01
影响因子：
3.3
通讯作者：
Xu, Hongyao
中科院分区：
文献类型：
--
作者：
Li, Linfeng;Wu, Rongliang;Xu, Hongyao
取代基和氢键在超分子自组装中起着重要作用。为了探索偶极-偶极诱导超分子自组装过程中氢键的影响机制，设计并合成了具有不同电负性和氢键能力的刚性偶氮苯分子.在温和的条件下，通过简单的求解过程构建了不同的规则形状的结构。实验结果和密度泛函理论计算都表明，弱的π-π堆积作用导致纳米柱的粗和短，强的偶极-偶极相互作用和偶极诱导的π-π堆积作用导致纳米棒的长和细，适当的氢键会加强偶极-偶极相互作用和偶极诱导的π-π堆积作用，形成薄的纳米片，而偶氮苯中过多的氢键会破坏规则形状的结构，产生不规则和随机的聚集体。即偶极-偶极相互作用驱动下偶氮苯纳米结构的生成存在一定的氢键饱和效应。结果表明，通过合理的分子设计，引入合适的偶极键和氢键，可以有效地控制偶氮苯结构有机材料的形貌。
The substituent group and hydrogen bonds play important roles in supramolecular self-assembly. To exploit the influential mechanism of hydrogen bonds during the dipole-dipole induced supramolecular self-assembly, some rigid azobenzene molecules with different electronegativity and hydrogen bonding capabilities were identified and designed. Different regular-shaped architectures were constructed via a simple solution process under mild conditions. Both experimental results and density functional theory calculations show that weak pi-pi stacking interactions lead to thick and short nanocylinders, strong dipole-dipole interactions and dipole induced pi-pi stacking lead to long and thin nanorods, appropriate hydrogen bonds consolidate the dipole-dipole interactions and dipole induced pi-pi stacking, forming thin nanosheets, while excessive hydrogen bonds in azobenzene would ruin the regular-shaped structures, giving irregular and stochastic aggregates. Namely there exists a certain hydrogen bond saturation effect in generating azobenzene nanostructures driven by dipole-dipole interactions. The results indicate that the morphologies of organic materials with azobenzene structures can be effectively controlled through rational molecular design by way of introducing appropriate dipole and hydrogen bonds.