First-Principles Study of Two Dimensional Transition Metal Phthalocyanine-Based Metal-Organic Frameworks in Kagome Lattice

Transition metal phthalocyanines (TMPc) and relevant derivatives can act as pervasive molecules for their electronic, magnetic, and optical applications. Numerous researches based on TMPc are carried out, attempting to synthesize novel two-dimensional (2D) metal-organic frameworks. Recently, some 2D poly-TMPc frameworks including FePc [J. Am. Chem. Soc. 133, 1203 (2011)], CoPc [Chem. Commun. 51, 2836 (2015)], and Ni-NiPc [J. Mater. Chem. A 6, 1188 (2018)] frameworks have been successfully synthesized experimentally. Meanwhile, potential applications in catalysis, gas storage, and spintronics were predicted by theoretical studies. Here, we propose a new kind of 2D poly-TMPc frameworks with kagome lattice (denoted as kag-TMPc) and systematically investigate their electronic and magnetic properties by employing first-principles calculations. We have demonstrated that the 2D kag-MnPc framework displays quite stable ferromagnetic ordering with Curie temperature about 125 K as indicated by Monte Carlo simulations based on Heisenberg model and prefers out-of-plane easy-magnetization axis. The 2D kag-CrPc framework is an ideal candidate for S=2 kagome antiferromagnet with RT3 magnetic order. Particularly, the investigations on optical absorption suggest that when the TMPc molecules are self-assembled into 2D kag- TMPc frameworks, their absorption wave bands are broadened, especially in visible region.

Single-Atom Protecting Group for on-Surface Synthesis of Graphdiyne Nanowires

On-surface synthesis of semiconducting graphdiyne nanowires usually su er severe side re- actions owing to the high reactivity of the butadiynylene units at noble metal surfaces, limiting the production of isolated nanowires. In this work, we report the high-yield synthesis of branchless graphdiyne nanowires [-C≡C-Ph2-C≡C-]n via on-surface Ullmann coupling of 1,4-bis(4-bromophenyl)-1,3-butadiyne molecules with chemical vapor deposition method. Non-contact atomic force microscopy with single-bond resolution reveals that single gold adatoms act as e ective protecting groups for butadiynylene units by forming Au-π ligand bonds, preventing unwanted branched coupling reactions and enabling the synthesis of ultralong isolated graphdiyne nanowires. This study will stimulate further investigation on the role of various surface adatoms in protecting on-surface reactions.

Controlling Metalation Reaction of Phthalocyanine with Cobalt at Single-Molecule Level on Au(111)Surfac

Metalation reac-tion of metal-free phthalocyanine molecule with Co atom adsorbed on Au(111)surface has been studied in situ at single atom/molecule scale by low-temperature scanning tunneling microscopy(STM)experiment combined with simulations based on density function theory calculations.Through manipulations using STM tip,we showed a controlled manner to have a single metal-free phthalocyanine molecule react with a Co atom to form Co phthalocyanine molecule.In this reaction process,an intermediate state originating from π-d interaction between the metal-free phthalocyanine molecule and Co atom has been identi ed.Moreover,we also revealed that the redox reaction represented as bond breaking and bond forming relative to the Co and pyrrolic N atoms,not pyrrolic H atoms,is a key process for dehydrogenation and metalation reaction.Our DFT calculations provided theoretical supporting for the above conclusions,and further understanding of the related mechanisms.

Epitaxial growth of highly strained antimonene on Ag（111）

The synthesis of antimonene, which is a promising group-V 2D material for both fundamental studies and technological applications, remains highly challenging. Thus far, it has been synthesized only by exfoliation or growth on a few substrates. In this study, we show that thin layers of antimonene can be grown on Ag（111） by molecular beam epitaxy. High-resolution scanning tunneling microscopy combined with theoretical calculations revealed that the submonolayer Sb deposited on a Ag（111） surface forms a layer of AgSb2 surface alloy upon annealing. Further deposition of Sb on the AgSb2 surface alloy causes an epitaxial layer of Sb to form, which is identified as antimonene with a buckled honeycomb structure. More interestingly, the lattice constant of the epitaxial antimonene （5 /-） is much larger than that of freestanding antimonene, indicating a high tensile strain of more than 20%. This kind of large strain is expected to make the antimonene a highly promising candidate for room- temperature quantum spin Hall material.

Observation of pseudogap in SnSe2 atomic layers grown on graphite

Superconducting metal dichalcogenides(MDCs)present several similarities to the other layered SI1-perconductors like cuprates.The superconductivity in atomically thin MDCs has been demonstrated by recent experiments,however,the investigation of the superconductivity intertwined with other or-ders are scarce.Investigating the pseudogap in atomic layers of MDCs may help to understand the superconducting mechanism for these true two dimensional(2D)superconducting systemns.Herein we report a pseudogap opening in the tunneling spectra of thin layers of SnSe2 epitaxially grown on highly oriented pyrolytic graphite(HOPG)with scanning tunneling microscopy/spectroscopy(STM/STS).A significant V-shaped pseudogap was observed to open near the Fermi level(Er)in the sTS.And at elevated temperatures,the gap gradually evolves to a shallow dip.Our experimental observations provide direct evidence of a pseudogap state in the electron-doped SnSe2 atomic layers on the HOPG surface,which may stimulate further exploration of the mechanism of superconductivity at 2D limit in MDCs.