On-surface synthesis of two types of cyano-substituted polyfluorene derivatives via Ullmann coupling on Au(111).

Using 4-(3,6-dibromo-9H-carbazol-9-yl)benzonitrile (DBCB) precursors, we successfully constructed two types of cyano-substituted polymers on Au(111) by the molecular beam epitaxy method. According to the geometry, the two polymers are referred to as w-type polymers composed of cis-dimers and z-type polymers composed of trans-dimers. The intermediate dimers and final polymers were well characterized by high-resolution scanning tunneling microscopy (HR-STM). Moreover, the productivities of these two polymers can be controlled by adjusting the heating rate and different treatment methods. High heating rates and hot deposition can provide more ample space and time for molecular diffusion, which is conducive to the formation of w-type polymers with relatively low density. In addition, by combining scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations, we have shown that the addition of CN groups reduces the band gap of the two polymers. Our investigation thus shows the controllable construction of nanostructures through efficient surface synthesis parameters and reveals the potential of using functional groups as tools to modify the electronic properties of polymers.

On-surface synthesis of Au-C4 and Au-O4 alternately arranged organometallic coordination networks via selective aromatic C-H bond activation.

Selective activation of the C-H bond of aromatic hydrocarbons is significant in synthetic chemistry. However, achieving oriented C-H activation remains challenging due to the poor selectivity of aromatic C-H bonds. Herein, we successfully constructed alternately arranged Au-C4 and Au-O4 organometallic coordination networks through selective aromatic C-H bond activation on Au(111) substrate. The stepwise reaction process of the 5, 12-dibromopyrene 3,4,9, 10-tetracarboxylic dianhydride precursor is monitored by high-resolution scanning tunneling microscopy. Our results show that the gold atoms in C-Au-C organometallic chains play a crucial role in promoting the selective ortho C-H bonds activation and forming Au-C4 coordination structure, which is further demonstrated by a comparative experiment of PTCDA precursor on Au(111). Furthermore, our experiment of 2Br-PTCDA precursor on Cu(111) substrate confirms that copper atoms in C-Cu-C organometallic chains can also assist the formation of Cu-C4 coordination structure. Our results reveal the vital effect of organometallic coordination on selective C-H bond activation of reactants, which holds promising implications for controllable on-surface synthesis.

Length-Dependent Magnetic Evolution of Anthenes on Au(111).

Nanographenes with zigzag edges, for example, anthenes, exhibit a unique nonbonding π-electron state, which can be described as a spin-polarized edge state that yields specific magnetic ground state. However, prior researches on the magnetism of anthenes with varying lengths on a surface is lacking. This study systematically fabricated anthenes with inherent zigzag carbon atoms of different lengths ranging from bisanthene to hexanthene. Their magnetic evolution on the Au(111) surface was analyzed through bond-resolved scanning probe techniques and density functional theory calculations. The analyses revealed a transition in magnetic properties associated with the length of the anthenes, arising from the imbalance between hybridization energy and the Coulomb repulsion between valence electrons. With the increasing length of the anthenes, the ground state transforms gradually from a closed-shell to an antiferromagnetic open-shell singlet, exhibiting a weak exchange coupling of 4 meV and a charge transfer-induced doublet. Therefore, this study formulated a chemically tunable platform to explore size-dependent π magnetism at the atomic scale, providing a framework for research in organic spintronics.

Adsorption configurations and electronic properties of self-assembled C60and C70molecules on a semiconductor CuSe monolayer with periodic nanopores.

Two-dimensional (2D) supramolecular self-assembly architectures are considered one of the most significant and challenging topics in nanotechnology and modern organic chemistry. The study of these processes on surfaces is vital to achieving a higher degree of control in the design of supramolecular architecture. Herein, we report on the 2D self-assembly monolayer architectures based on C60and C70molecules on a semiconductor CuSe monolayer with periodic nanopores, which are essential for providing ideas for surface template chemistry. With the aid of low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/STS) and density functional theory (DFT) calculation methods, we systematically investigate the adsorption configurations and electronic properties of C60and C70on CuSe monolayer with periodic nanopores. Our results show that both the C60and C70molecules above the nanopores will fall into the nanopores, while those on the CuSe surface will show well-defined self-assembly with various adsorption configurations. Besides, through STS measurement, the lowest unoccupied molecular orbitals (LUMOs) and characteristic peaks of fullerene molecules will be slightly different due to different adsorption configurations. This work helps us to study the adsorption behavior of the fullerene family on various kinds of semiconductor substrates, and also provides vigorous support for the development of fullerene electrical devices in the future.

Controllable fabrication and photocatalytic performance of nanoscale single-layer MoSe2 islands with substantial edges on an Ag(111) substrate.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are emerging as new electrocatalysts and photocatalysts. The edge sites of 2D TMDs show high catalytic activity and are thus favored at the catalyst surface over TMD inert basal planes. However, 2D TMDs that predominantly expose edges are thermodynamically unfavorable, limiting the number of edge sites at the surface. Herein, we demonstrate a controllable synthesis strategy of single-layer 2D MoSe2 islands with a lateral size of approximately 5-12 nm on an Ag(111) substrate by pre-deposition of excess Se atoms. The surplus Se atoms react with the Ag(111) substrate and form silver selenide compounds to separate MoSe2 islands and further prevent MoSe2 islands from growing up. The nanoscale MoSe2 islands greatly increase the ratio of exposed edge sites relative to the basal plane sites, which leads to excellent photocatalytic activity for the degradation of a methylene blue (MB) organic pollutant. This work paves the way to limit the size of 2D TMDs at the nanoscale and enables new opportunities for enhancing the catalytic activity of 2D TMD materials.