Template-controlled on-surface synthesis of a lanthanide supernaphthalocyanine and its open-chain polycyanine counterpart
Template-controlled on-surface synthesis of a lanthanide supernaphthalocyanine and its open-chain polycyanine counterpart
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DOI：
10.1038/s41467-019-13030-7
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发表时间：
2019-11-06
影响因子：
16.6
通讯作者：
Gottfried，J. Michael
中科院分区：
文献类型：
--
作者：
Fan，Qitang;Luy，Jan-Niclas;Gottfried，J. Michael
酞菁类化合物具有独特的光学和电学性质，在光电子器件、涂料、光动力学治疗等方面有着广泛的应用。拓展酞菁类化合物的π-电子体系可以制备出具有红移吸收的分子材料，具有更广泛的应用前景。然而，由于有限的合成可能性，获得具有多于四个异吲哚啉单元的扩展酞菁类似物具有挑战性。在这里，我们报告的控制上的表面合成的钆supernaphthalocycles大环和它的开链对应物聚（苯并二亚氨基异吲哚啉）的银表面从萘二甲腈前体。它们的形成由表面上的高稀释原理控制，并由不同的金属模板控制，即，钆原子和裸露的银表面，其也充当低聚催化剂。利用扫描隧道显微镜、光电子能谱和密度泛函理论计算，对这些具有扩展π共轭结构的酞菁类似物的化学结构、力学和电子性质进行了沿着研究.
Phthalocyanines possess unique optical and electronic properties and thus are widely used in (opto)electronic devices, coatings, photodynamic therapy, etc. Extension of their π-electron systems could produce molecular materials with red-shifted absorption for a broader range of applications. However, access to expanded phthalocyanine analogues with more than four isoindoline units is challenging due to the limited synthetic possibilities. Here, we report the controlled on-surface synthesis of a gadolinium-supernaphthalocyanine macrocycle and its open-chain counterpart poly(benzodiiminoisoindoline) on a silver surface from a naphthalene dicarbonitrile precursor. Their formation is controlled by the on-surface high-dilution principle and steered by different metal templates, i.e., gadolinium atoms and the bare silver surface, which also act as oligomerization catalysts. By using scanning tunneling microscopy, photoemission spectroscopy, and density functional theory calculations, the chemical structures along with the mechanical and electronic properties of these phthalocyanine analogues with extended π-conjugation are investigated in detail.