Mateo Luis M, Sun Qiang, Eimre Kristjan, Pignedoli Carlo A, Torres Tomas, Fasel Roman, Bottari Giovanni
Departamento de Química Orgánica, Universidad Autónoma de Madrid 28049 Madrid Spain
IMDEA-Nanociencia Campus de Cantoblanco 28049 Madrid Spain.
Chem Sci. 2020 Oct 26;12(1):247-252. doi: 10.1039/d0sc04316h.
On-surface synthesis has emerged as a powerful tool for the construction of large, planar, π-conjugated structures that are not accessible through standard solution chemistry. Among such solid-supported architectures, graphene nanoribbons (GNRs) hold a prime position for their implementation in nanoelectronics due to their manifold outstanding properties. Moreover, using appropriately designed molecular precursors, this approach allows the synthesis of functionalized GNRs, leading to nanostructured hybrids with superior physicochemical properties. Among the potential "partners" for GNRs, porphyrins (Pors) outstand due to their rich chemistry, robustness, and electronic richness, among others. However, the use of such π-conjugated macrocycles for the construction of GNR hybrids is challenging and examples are scarce. Herein, singly and doubly Por-capped GNR segments presenting a commensurate and triply-fused GNR-Por heterojunction are reported. The study of the electronic properties of such hybrid structures by high-resolution scanning tunneling microscopy, scanning tunneling spectroscopy, and DFT calculations reveals a weak hybridization of the electronic states of the GNR segment and the Por moieties despite their high degree of conjugation.
表面合成已成为构建大型平面π共轭结构的有力工具,这些结构无法通过标准溶液化学方法获得。在这类固体支撑结构中,石墨烯纳米带(GNRs)因其多种优异性能在纳米电子学中的应用而占据首要地位。此外,使用经过适当设计的分子前体,这种方法能够合成功能化的GNRs,从而得到具有优异物理化学性质的纳米结构杂化物。在GNRs的潜在“伙伴”中,卟啉(Pors)因其丰富的化学性质、稳定性和电子丰富性等脱颖而出。然而,使用这种π共轭大环构建GNR杂化物具有挑战性,相关实例很少。在此,报道了具有匹配且三重融合的GNR-Por异质结的单卟啉和双卟啉封端的GNR片段。通过高分辨率扫描隧道显微镜、扫描隧道光谱和密度泛函理论计算对这类杂化结构电子性质的研究表明,尽管GNR片段和卟啉部分具有高度共轭性,但它们的电子态杂化较弱。