Synthesis and Electronic Properties of Directly Linked Dihydrodiazatetracene Dimers
Synthesis and Electronic Properties of Directly Linked Dihydrodiazatetracene Dimers
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直连二氢氮杂并四苯二聚体的合成及电子性质
DOI：
10.1002/chem.202005005
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发表时间：
2021
期刊：
影响因子：
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通讯作者：
Fujiwara Hideki
中科院分区：
文献类型：
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作者：
Tanaka Katsuki;Sakamaki Daisuke;Fujiwara Hideki
合成了具有不同取代模式的5，12-二氢-5，12-二氮杂四苯（DHDAT）二聚体：单体单元之间具有C-C键的对称二聚体（1）和单体单元之间具有C-N键的两个不对称二聚体（2和3）。DHDAT单元在C-C连接的二聚体1中是平面的，但在C-N连接的二聚体2和3中是垂直取向的（来自X射线分析）。两个单元之间的电子基态相互作用在1中很大，在2和3中很小。3的发光行为不同于其他二聚体及其单体，尽管它具有给体-给体型结构，但它显示出正的溶剂化变色，这是电子给体-受体分子的特征。化合物3表现出独特的多步热致变色发射行为。发光行为归因于DHDAT的HOMO和LUMO的不对称分布。
5,12‐Dihydro‐5,12‐diazatetracene (DHDAT) dimers with different substitution patterns are synthesized: a symmetric one with a C−C bond between the monomer units (1) and two asymmetric ones with a C−N bond between the monomer units (2and3). The DHDAT units are planar in the C−C linked dimer1but perpendicularly oriented in the C−N linked dimers2and3(from X‐ray analysis). The electronic ground‐state interaction between the two units is large in1and small in2and3. The emission behavior of3is different from that of other dimers and its monomer; it displays positive solvatochromism, characteristic for electron donor–acceptor molecules, despite its donor–donor type structure. Compound3exhibits a unique multi‐step thermochromic emission behavior. The emission behavior is attributed to the asymmetric distribution of the HOMO and LUMO of DHDAT.