Donors and acceptors based on triangular dehydrobenzo[12]annulenes: formation of a triple-layered rosette structure by a charge-transfer complex.
Donors and acceptors based on triangular dehydrobenzo[12]annulenes: formation of a triple-layered rosette structure by a charge-transfer complex.
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DOI：
10.1021/ja804604y
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发表时间：
2008-09
影响因子：
15
通讯作者：
Kazukuni Tahara;T. Fujita;M. Sonoda;M. Shiro;Y. Tobe
中科院分区：
文献类型：
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作者：
Kazukuni Tahara;T. Fujita;M. Sonoda;M. Shiro;Y. Tobe
我们在此介绍基于三角脱氢苯并[12]轮烯（[12]DBA）体系作为π核的供体和受体的合成和性质的研究结果。这些研究旨在控制超分子晶体结构。为此，合成了三氰基[12]DBA 2和十二氟[12]DBA（3）作为受体（A），三（二烷基氨基）[12]DBA 4a-d作为供体（D），并通过电子吸收光谱和电化学测量确定了它们的电子性质。不过，主要焦点是晶体中超分子结构的形成。由于不同的分子间相互作用，这些化合物形成不同的堆积模式。 Tricyano[12]DBA 2 通过氢键相互作用形成二维 (2D) 片状结构，而 3 由于缺乏显着的分子间相互作用而形成倾斜堆叠结构。 Tris(二丁基氨基)[12]DBA 4b 表现出梯型二维结构，可能是由于丁基之间的范德华相互作用。最重要的发现是，供体 4a 和受体 3 之间的电荷转移相互作用，结合它们的三角形分子形状和横向 CH...F 氢键，导致形成二维玫瑰花结结构，该结构由两种不同的三聚体（DAD 型和 ADA 型）夹心结构组成，A/D 比例分别为 1:2 和 2:1。
We present here the results of studies of the synthesis and properties of donors and acceptors based on triangular dehydrobenzo[12]annulene ([12]DBA) system as a pi core. These studies were aimed at controlling the supramolecular crystal structure. Toward this end, the tricyano[12]DBA 2 and dodecafluoro[12]DBA ( 3) were synthesized as acceptors (A) and the tris(dialkylamino)[12]DBAs 4a-d as donors (D), and their electronic properties were determined by electronic absorption spectroscopy and electrochemical measurements. The main focus, though, was the formation of supramolecular structures in crystals. These compounds form distinct packing patterns as a result of the different intermolecular interactions. Tricyano[12]DBA 2 forms a two-dimensional (2D) sheet structure via hydrogen-bonding interactions, whereas a tilted-stack structure was found for 3 because of the lack of significant intermolecular interactions. Tris(dibutylamino)[12]DBA 4b exhibits a ladder-type 2D structure, probably because of van der Waals interactions between the butyl groups. The most significant finding is that charge-transfer interactions between donor 4a and acceptor 3 combined with their triangular molecular shapes and lateral CH...F hydrogen bonding result in the formation of a 2D rosette structure consisting of two different trimeric (DAD- and ADA-type) sandwich structures with 1:2 and 2:1 A/D ratios, respectively.