Modulation of supramolecular structure by stepwise removal of tert-butyl groups from tetraazaperopyrene derivatives on Ag(111).

Tert-butyl functional groups can modulate the self-assembly behavior of organic molecules on surfaces. However, the precise construction of supramolecular architectures through their controlled thermal removal remains a challenge. Herein, we precisely controlled the removal amount of tert-butyl groups in tetraazaperopyrene derivatives by stepwise annealing on Ag(111). The evolution of 4tBu-TAPP supramolecular self-assembly from the grid-like structure composed of 3tBu-TAPP through the honeycomb network formed by 2tBu-TAPP to the one-dimensional chain co-assembled by tBu-TAPP and TAPP was successfully realized. This series of supramolecular nanostructures were directly visualized by high resolution scanning tunneling microscopy. Tip manipulation and density functional theory calculations show that the formation of honeycomb network structure can be attributed to the van der Waals interactions, N-Ag-N coordination bonds, and weak C-H⋯N hydrogen bonds. Further addition of two tert-butyl groups (6tBu-TAPP) leads to a completely different assembly evolution, due to the fact that the additional tert-butyl groups affect the molecular adsorption behavior and ultimately induce desorption. This work can possibly be exploited in constructing stable and long-range ordered nanostructures in surface-assisted systems, which can also promote the development of nanostructures in functional molecular devices.

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.

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.

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.

Highly Regioselective Cyclodehydrogenation of Diphenylporphyrin on Metal Surfaces.

Exploring the effect of porphin tautomerism on the regioselectivity of its derivatives is a big challenge, which is significant for the development and application of porphyrin drugs. In this work, we demonstrate the regioselectivity of 2H-diphenylporphyrin (H2-DPP) in the planarization reaction on Au(111) and Ag(111) substrates. H2-DPP monomer forms two configurations (anti- and syn-) via a dehydrogenation coupling, between which the yield of the anti-configuration exceeds 90%. Using high-resolution scanning tunneling microscopy, we visualize the reaction processes from the H2-DPP monomer to the final two planar products. Combined with DFT calculations of the potential reaction pathway and comparative experiments on Au(111) and Ag(111) substrates. Using M-DPP (M = Cu and Fe), we confirm that the regioselectivity of H2-DPP is derived from the reaction energy barrier during the cyclodehydrogenation reaction of different tautomers. This work reveals the regioselectivity mechanism of H2-DPP on the atomic scale, which holds great significance for understanding the chemical conversion process of organic macrocyclic molecules.

Enhancement of Mass and Charge Transfer during Carbon Dioxide Photoreduction by Enhanced Surface Hydrophobicity without a Barrier Layer.

The CO2 reduction reaction (CRR) represents a promising route for the clean utilization of renewable resources. But mass-transfer limitations seriously hinder the forward step. Enhancing the surface hydrophobicity by using polymers has been proved to be one of the most efficient strategies. However, as macromolecular organics, polymers on the surface hinder the transfer of charge carriers from catalysts to reactants. Herein, we describe an in-situ surface fluorination strategy to enhance the surface hydrophobicity of TiO2 without a barrier layer of organics, thus facilitating the mass transfer of CO2 to catalysts and charge transfer. With less obstruction to charge transfer, a higher CO2, and lower H+ surface concentration, the photocatalytic CRR generation rate of methanol (CH3 OH) is greatly enhanced to up to 247.15 µmol g-1 h-1 . Furthermore, we investigated the overall defects; enhancing the surface hydrophobicity of catalysts provides a general and reliable method to improve the competitiveness of CRR.

Extraction, Identification, Modification, and Antibacterial Activity of Histone from Immature Testis of Atlantic salmon.

In the present study, histone from immature testis of Atlantic salmon was extracted and identified, and its antibacterial activity after enzymolysis was investigated. Histone extracted from Atlantic salmon (Salmo salar) testis using the acid extraction method was successfully identified by LC-MS/MS, and revealed significant inhibitory activity on both the Gram-negative and Gram-positive bacteria. With a low concentration of 10 mg/mL, the observed inhibitory zone diameter (IZD) could significantly reach up to 15.23 mm. After modification of enzymatic hydrolysis by pepsin, histone could be digested to three fragments, while the antibacterial activity increased up to 57.7%. All the results suggested the leftovers from commercial fishing could be utilized for the extraction of antimicrobial peptides.