通过调节π-π相互作用的强弱构筑生长方向可控的金属配位超分子自组装体系
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- 英文论文题名：Constructing Direction Controllable Metallosupermolecular Self-assemble System via Adjusting the Strength of π-π Interaction
- 论文作者：吴峥 ; 黄建滨 ; 阎云
- 英文论文作者：Zheng Wu ; Jianbin Huang ; Yunyan ; College of Chemistry and Molecular Engineering ; Peking University
- 年：2016
- 作者机构：北京大学化学与分子工程学院;
- 论文关键词：偶氮苯 ; 自组装 ; 配位作用 ; π-π相互作用 ; 组装方向
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十一分会：胶体与界面化学
- 语种：中文
- 分类号：O641
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十一分会 ; 胶体与界面化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：313k
- 原文格式：D
- 会议级别：全国
摘要
在我组之前的工作中,我们通过双头配体TPE-C4-L2与金属之间的配位相互作用与π-π相互作用构筑了具有严格周期性排列结构的聚离子自组装体。在组装过程中,由于TPE典型的螺旋桨型结构,TPE-C4-L2分子之间的π-π相互作用很弱,这就使得聚集体向配位相互作用方向生长,得到在低温电镜下有横向条纹的"纳米梯子"。基于这个结果,我们设想,如果我们引入π-π相互作用强的中心基团,比如偶氮苯基团,我们就能控制聚集体的生长方向,使之向π-π相互作用的方向生长,也就是垂直于先前TPE-C4-L2聚集体生长方向,得到结构规整具有纵向条纹的"纳米轨道"。另外,由于在该聚集体中,偶氮苯分子堆叠紧密,形成H-聚集体,不能为反式向顺式的转变提供足够的空间,使得偶氮苯光致异构化的性质被大大抑制,这种结构特征在制作高稳定性染料领域将有重要应用。
In our previous work,we have reported the formation of polyion assemblies with well-defined,periodically regular internal structure by imparting the proper stiffness to the molecular tile.A stiff bisligand TPE-C4-L2 was designed which is able to form a negatively charged supramolecular polyelectrolyte which can slowly self-assemble into polydispersed flat cocoon-like sheets with transition metal ions Ni~(2+).Since the propeller shape of TPE group,the π-π interaction among TPE-C4-L2 molecules is very weak,which made the aggregation grow towards the direction of the coordination.Based on this result,we wondered if we change the center group with which could introduce stronger π-π interaction,maybe we could control the growing direction of the aggregations,make them develop towards the direction of the π-π interaction,namely,perpendicular to the coordination direction,it must be very interesting.In this work,we choosed azobenzene as our new center group due to its strong intermolecular π-πinteraction and typical optical properties,and we had successfully gotten a strikingly fine "orbit"-like periodic ribbon system developing towards the direction of π-π interaction.
In our previous work,we have reported the formation of polyion assemblies with well-defined,periodically regular internal structure by imparting the proper stiffness to the molecular tile.A stiff bisligand TPE-C4-L2 was designed which is able to form a negatively charged supramolecular polyelectrolyte which can slowly self-assemble into polydispersed flat cocoon-like sheets with transition metal ions Ni~(2+).Since the propeller shape of TPE group,the π-π interaction among TPE-C4-L2 molecules is very weak,which made the aggregation grow towards the direction of the coordination.Based on this result,we wondered if we change the center group with which could introduce stronger π-π interaction,maybe we could control the growing direction of the aggregations,make them develop towards the direction of the π-π interaction,namely,perpendicular to the coordination direction,it must be very interesting.In this work,we choosed azobenzene as our new center group due to its strong intermolecular π-πinteraction and typical optical properties,and we had successfully gotten a strikingly fine "orbit"-like periodic ribbon system developing towards the direction of π-π interaction.
引文
[1]Xu,Limin;Huang,Jianbin*;Yan,Yun*,J.Am.Chem.Soc.2014,136,1942–1947
[2]Masaki Yamamura*,Chem.Eur.J.2014,20,16258–16265
[2]Masaki Yamamura*,Chem.Eur.J.2014,20,16258–16265