A Cu2(C6O6) metal-organic framework monolayer assembled on silicon carbide grown graphene exhibiting a metallic band structure.

We report the self-assembly of a monolayer metal-organic framework of Cu-benzenehexol (BHO) on a graphene/SiC substrate assisted by in situ Cu-catalyzed deprotonation reactions. The density functional theory calculations reveal that the free-standing framework is a semiconductor with a band gap of 0.485 eV. Interestingly, upon adsorption on the substrate, the Fermi level is up-shifted to the conduction band of the free-standing framework due to the n-doped graphene on SiC, while the other band structure features are largely preserved. The metallic nature corroborates the scanning tunneling microscopy images acquired near the Fermi level. This work demonstrates that the graphene substrate, which interacts weakly with the framework, can be used to tune the Fermi level of the metal-organic framework.

In situ generation of acyloxyphosphoniums for mild and efficient synthesis of thioesters.

We present a novel approach for in situ generation of acyloxyphosphoniums by premixing iodobenzene dicarboxylates and triphenylphosphine, resulting in efficient thioester synthesis (up to 100% yield). Stable solid iodobenzene dicarboxylates, achieved via carboxylate exchange, serve as hypervalent iodine precursors. The resulting acyloxyphosphoniums allow convenient one-pot thioester synthesis under mild conditions. Our method demonstrates facile acyloxyphosphonium production from iodobenzene dicarboxylates and Ph3P, enabling diverse thioester preparation. ESI-MS analysis confirms acyloxyphosphonium ion formation, pivotal in acylation. This strategy holds potential for combinatorial thioester synthesis and broader nucleophile modification applications.

Giant nonlinear Hall effect in twisted bilayer WSe2.

The recently discovered nonlinear Hall effect (NHE) in a few non-interacting systems provides a novel mechanism for generating second-harmonic electrical Hall signals under time-reversal-symmetric conditions. Here, we introduce a new approach to engineering an NHE by using twisted moiré structures. We found that the twisted WSe2 bilayer exhibited an NHE when the Fermi level was tuned to the moiré flat bands. When the first moiré band was half-filled, the nonlinear Hall signal exhibited a sharp peak with a generation efficiency that was at least two orders of magnitude greater than those obtained in previous experiments. We discuss the possible origins of the diverging generation efficiency in twisted WSe2 based on resistivity measurements, such as moiré-interface-induced correlation effects and mass-diverging-type continuous Mott transition. This study demonstrates not only how interaction effects can combine with Berry curvature dipoles to produce novel quantum phenomena, but also the potential of NHE measurements as a new tool for studying quantum criticality.

A p-orbital honeycomb-Kagome lattice realized in a two-dimensional metal-organic framework.

The experimental realization of p-orbital systems is desirable because p-orbital lattices have been proposed theoretically to host strongly correlated electrons that exhibit exotic quantum phases. Here, we synthesize a two-dimensional Fe-coordinated bimolecular metal-organic framework which constitutes a honeycomb lattice of 1,4,5,8,9,12-hexaazatriphenylene molecules and a Kagome lattice of 5,15-di(4-pyridyl)-10,20-diphenylporphyrin molecules on a Au(111) substrate. Density-functional theory calculations show that the framework features multiple well-separated spin-polarized Kagome bands, namely Dirac cone bands and Chern flat bands, near the Fermi level. Using tight-binding modelling, we reveal that these bands are originated from two effects: the low-lying molecular orbitals that exhibit p-orbital characteristics and the honeycomb-Kagome lattice. This study demonstrates that p-orbital Kagome bands can be realized in metal-organic frameworks by using molecules with molecular orbitals of p-orbital like symmetry.

On-Surface-Assembled Single-Layer Metal-Organic Frameworks with Extended Conjugation.

Single-layer metal-organic frameworks with extended conjugation (SL-cMOFs) exhibit electronic bands that lead to high conductivity or non-trivial quantum phases. Experimental realization of SL-cMOFs has been demonstrated using on-surface coordination self-assembly. The tunability and adaptability of coordination assembly offers rich opportunities for designing and fabricating SL-cMOFs with various geometric characteristics. In this Review, we discuss the recent experimental advances in on-surface synthesis of SL-cMOFs and characterization of their band structures. Special attention has been paid to the MOFs featuring Kagome lattices. Starting from the general principles of their structural design, the SL-cMOFs recently achieved via on-surface coordination self-assembly are subsequently divided into three categories, that is, M3 L2 , M2 L3 , and M3 L MOFs (M for metal and L for ligand), and the corresponding works are overviewed. The current challenges and prospective directions are also discussed.

Low-defect-density WS2 by hydroxide vapor phase deposition.

Two-dimensional (2D) semiconducting monolayers such as transition metal dichalcogenides (TMDs) are promising channel materials to extend Moore's Law in advanced electronics. Synthetic TMD layers from chemical vapor deposition (CVD) are scalable for fabrication but notorious for their high defect densities. Therefore, innovative endeavors on growth reaction to enhance their quality are urgently needed. Here, we report that the hydroxide W species, an extremely pure vapor phase metal precursor form, is very efficient for sulfurization, leading to about one order of magnitude lower defect density compared to those from conventional CVD methods. The field-effect transistor (FET) devices based on the proposed growth reach a peak electron mobility ~200 cm2/Vs (~800 cm2/Vs) at room temperature (15 K), comparable to those from exfoliated flakes. The FET device with a channel length of 100 nm displays a high on-state current of ~400 µA/µm, encouraging the industrialization of 2D materials.

Synthesis of Single-Layer Two-Dimensional Metal-Organic Frameworks M3 (HAT)2 (M=Ni, Fe, Co, HAT=1,4,5,8,9,12-hexaazatriphenylene) Using an On-Surface Reaction.

1,4,5,8,9,12-Hexaazatriphenylene (HAT) is one of the smallest polyheterocyclic aromatic building blocks for forming conjugated metal-organic frameworks (cMOFs). However, the strong inter-molecular steric hindrance impedes the growth of HAT-based cMOFs. Here we employ on-surface synthesis to grow single-layer two-dimensional cMOFs of M3 (HAT)2 (M=Ni, Fe, Co). Using scanning tunnelling microscopy and density-functional theory (DFT) analysis, we resolve that the frameworks comprise a hexagonal lattice of HAT molecules and a Kagome lattice of metal atoms. The DFT analysis indicates that Ni, Co and Fe carry a magnetic moment of 1.1, 2.5, and 3.7 µB, respectively. We anticipate that the small π-conjugated core of HAT and strong bidentate chelating coordination give rise to appealing electronic and magnetic properties.

On-Surface Synthesis: A New Route Realizing Single-Layer Conjugated Metal-Organic Structures.

Recently, both experimental and theoretical advances have demonstrated that two-dimensional conjugated metal-organic frameworks (2D-cMOFs) exhibit interesting electronic and magnetic properties, such as high conductivity and ferromagnetism. Theoretical studies have predicted that exotic quantum states, including topological insulating states and superconductivity, emerge in some 2D-MOFs. The high design tunability of MOFs' structure and composition provides great opportunities to realize these structures. However, most conventional synthesis methods yield multilayer structures of the 2D-cMOFs, in which the predicted exotic quantum phases are often quenched because of interlayer interactions. It is highly desirable to synthesize single-layer cMOFs. On-surface synthesis represents a novel strategy toward this goal. In this Perspective, we discuss the recent developments in on-surface synthesis of 1D- and 2D-cMOFs.

On-surface synthesis and spontaneous segregation of conjugated tetraphenylethylene macrocycles.

Creating conjugated macrocycles has attracted extensive research interest because their unique chemical and physical properties, such as conformational flexibility, intrinsic inner cavities and aromaticity/antiaromaticity, make these systems appealing building blocks for functional supramolecular materials. Here, we report the synthesis of four-, six- and eight-membered tetraphenylethylene (TPE)-based macrocycles on Ag(111) via on-surface Ullmann coupling reactions. The as-synthesized macrocycles are spontaneously segregated on the surface and self-assemble as large-area two-dimensional mono-component supramolecular crystals, as characterized by scanning tunneling microscopy (STM). We propose that the synthesis benefits from the conformational flexibility of the TPE backbone in distinctive multi-step reaction pathways. This study opens up opportunities for exploring the photophysical properties of TPE-based macrocycles.

Lattice reconstruction induced multiple ultra-flat bands in twisted bilayer WSe2.

Moiré superlattices in van der Waals heterostructures provide a tunable platform to study emergent properties that are absent in the natural crystal form. Twisted bilayer transition metal dichalcogenides (TB-TMDs) can host moiré flat bands over a wide range of twist angles. For twist angle close to 60°, it was predicted that TB-TMDs undergo a lattice reconstruction which causes the formation of ultra-flat bands. Here, by using scanning tunneling microscopy and spectroscopy, we show the emergence of multiple ultra-flat bands in twisted bilayer WSe2 when the twist angle is within 3° of 60°. The ultra-flat bands are manifested as narrow tunneling conductance peaks with estimated bandwidth less than 10 meV, which is only a fraction of the estimated on-site Coulomb repulsion energy. The number of these ultra-flat bands and spatial distribution of the wavefunctions match well with the theoretical predictions, strongly evidencing that the observed ultra-flat bands are induced by lattice reconstruction. Our work provides a foundation for further study of the exotic correlated phases in TB-TMDs.

Benchmarking of eight recurrent neural network variants for breath phase and adventitious sound detection on a self-developed open-access lung sound database-HF_Lung_V1.

A reliable, remote, and continuous real-time respiratory sound monitor with automated respiratory sound analysis ability is urgently required in many clinical scenarios-such as in monitoring disease progression of coronavirus disease 2019-to replace conventional auscultation with a handheld stethoscope. However, a robust computerized respiratory sound analysis algorithm for breath phase detection and adventitious sound detection at the recording level has not yet been validated in practical applications. In this study, we developed a lung sound database (HF_Lung_V1) comprising 9,765 audio files of lung sounds (duration of 15 s each), 34,095 inhalation labels, 18,349 exhalation labels, 13,883 continuous adventitious sound (CAS) labels (comprising 8,457 wheeze labels, 686 stridor labels, and 4,740 rhonchus labels), and 15,606 discontinuous adventitious sound labels (all crackles). We conducted benchmark tests using long short-term memory (LSTM), gated recurrent unit (GRU), bidirectional LSTM (BiLSTM), bidirectional GRU (BiGRU), convolutional neural network (CNN)-LSTM, CNN-GRU, CNN-BiLSTM, and CNN-BiGRU models for breath phase detection and adventitious sound detection. We also conducted a performance comparison between the LSTM-based and GRU-based models, between unidirectional and bidirectional models, and between models with and without a CNN. The results revealed that these models exhibited adequate performance in lung sound analysis. The GRU-based models outperformed, in terms of F1 scores and areas under the receiver operating characteristic curves, the LSTM-based models in most of the defined tasks. Furthermore, all bidirectional models outperformed their unidirectional counterparts. Finally, the addition of a CNN improved the accuracy of lung sound analysis, especially in the CAS detection tasks.

Highly Degenerate Ground States in a Frustrated Antiferromagnetic Kagome Lattice in a Two-Dimensional Metal-Organic Framework.

Realization of the Kagome antiferromagnetic (KAF) lattice is of high interest because the geometric frustration in the Kagome lattice is expected to give rise to highly degenerated ground states that may host exotic phases such as quantum spin liquid. Here we demonstrate the design and synthesis of a single-layer two-dimensional metal-organic framework (2D-MOF) containing a Kagome lattice of Fe(II) ions assembled on a Au(111) surface. First-principles calculations reveal that the Fe(II) ions are at a high spin state of S = 2 and are coupled antiferromagnetically with nearest-neighboring exchange J1 = 5.8 meV. The ground state comprises various degenerated spin configurations including the well-known q = 0 and q = √3 × âˆš3 phases. Remarkably, we observe a spin excitation at 6 meV using tunneling spectroscopy. This work points out a feasible route toward realizing spin 1/2 KAF, a candidate quantum spin liquid system, by replacing Fe(II) by Cu(II) in the same structure.

Investigation of edge states in artificial graphene nano-flakes.

Graphene nano-flakes (GNFs) are predicted to host spin-polarized metallic edge states, which are envisioned for exploration of spintronics at the nanometer scale. To date, experimental realization of GNFs is only in its infancy because of the limitation of precise cutting or synthesizing methods at the nanometer scale. Here, we use low temperature scanning tunneling microscope to manipulate coronene molecules on a Cu(111) surface to build artificial triangular and hexagonal GNFs with either zigzag or armchair type of edges. We observe that an electronic state at the Dirac point emerges only in the GNFs with zigzag edges and localizes at the outmost lattice sites. The experimental results agree well with the tight-binding calculations. Our work renders an experimental confirmation of the predicated edge states of the GNFs.

Lung ventilation distribution in patients after traditional full sternotomy and minimally invasive thoracotomy: An observational study.

BACKGROUND: The aim of the study was to examine the post-operative ventilation distribution changes in cardiac surgical patients after traditional full sternotomy (FS) or minimally invasive thoracotomy (MIT). METHODS: A total of 40 patients scheduled for FS with two-lung ventilation or MIT with one-lung ventilation were included. Ventilation distribution was measured with electrical impedance tomography (EIT) at T1, before surgery; T2, after surgery in ICU before weaning; T3, 24 hours after extubation. EIT-based parameters were calculated to assess the ventilation distribution, including the left-to-right lung ratio, ventral-to-dorsal ratio, and the global inhomogeneity index. RESULTS: The global inhomogeneity index increased at T2 and T3 compared to T1 in all patients but only statistically significant in patients with MIT (FS, P = .06; MIT, P < .01). Notable decrease in the dorsal regions (FS) or in the non-ventilated side (MIT) was observed at T2. Ventilation distribution was partially improved at T3 but huge variations of recovery progresses were found in all patients regardless of the surgery types. Subgroup analysis indicated that operation duration was significantly lower in the MIT group (240 ± 40 in FS vs 205 ± 90 minutes in MIT, median ± interquartile range, P < .05) but the incidence of atrial fibrillation/flutter was significantly higher (5% in FS vs 50% in MIT, P < .01). Other exploratory outcomes showed no statistical differences. CONCLUSIONS: Ventilation distribution was impaired after cardiac surgery. The recovery process of ventilation homogeneity was strongly depending on individuals so that MIT was not always superior in this aspect. EIT may help to identify the patients requiring further care after surgery.

Collective Spin Manipulation in Antiferroelastic Spin-Crossover Metallo-Supramolecular Chains.

Coupled spin-crossover complexes in supramolecular systems feature rich spin phases that can exhibit collective behaviors. Here, we report on a molecular-level exploration of the spin phase and collective spin-crossover dynamics in metallo-supramolecular chains. Using scanning tunneling microscopy, spectroscopy, and density functional theory calculations, we identify an antiferroelastic phase in the metal-organic chains, where the Ni atoms coordinated by deprotonated tetrahydroxybenzene linkers on Au(111) are at a low-spin (S = 0) or a high-spin (S = 1) state alternately along the chains. We demonstrate that the spin phase is stabilized by the combined effects of intrachain interactions and substrate commensurability. The stability of the antiferroelastic structure drives the collective spin-state switching of multiple Ni atoms in the same chain in response to electron/hole tunneling to a Ni atom via a domino-like magnetostructural relaxation process. These results provide insights into the magnetostructural dynamics of the supramolecular structures, offering a route toward their spintronic manipulations.

On-surface Synthesis of a Semiconducting 2D Metal-Organic Framework Cu3 (C6 O6 ) Exhibiting Dispersive Electronic Bands.

A 2D metal-organic framework (2D-MOF) was formed on a Cu(111) substrate using benzenehexol molecules. By means of a combination of scanning tunneling microscopy and spectroscopy, X-ray photoelectron spectroscopy and density-functional theory, the structure of the 2D-MOF is determined to be Cu3 (C6 O6 ), which is stabilized by O-Cu-O bonding motifs. We find that upon adsorption on Cu(111), the 2D-MOF features a semiconductor band structure with a direct band gap of 1.5 eV. The O-Cu-O bonds offer efficient charge delocalization, which gives rise to a highly dispersive conduction band with an effective mass of 0.45 me at the band bottom, implying a high electron mobility in this material.

Identifying Multinuclear Organometallic Intermediates in On-Surface [2+2] Cycloaddition Reactions.

We investigate the on-surface [2+2] cycloaddition reaction of 2,3,6,7,10,11-hexabromotriphenylene (HBTP) on Ag(111), Cu(111), Au(111), and Cu-dosed Au(111) surfaces using STM and DFT simulation focusing on the organometallic intermediates. The fully debrominated HBTP molecules form an organo-silver framework on Ag(111) and an organo-copper framework on Cu(111), both incorporating multinuclear metal adatom clusters. The organo-silver framework is converted into porous covalent networks via [2+2] cycloaddition above 240 °C. In contrast, the organo-copper framework is very stable and does not undergo [2+2] cycloaddition even at 300 °C. On Au(111), no organo-gold intermediate of [2+2] cycloaddition is observed. After loading Cu onto Au(111), the partially debrominated HBTP molecules bind to Cu adatom dimers to form multinuclear organo-copper complexes at 100 °C which undergo [2+2] cycloaddition at 140 °C. This study shows that the choice of surface can direct the reaction pathway.

Kinetically Controlled Synthesis of Four- and Six-Member Cyclic Products via Sequential Aryl-Aryl Coupling on a Au(111) Surface.

We synthesize four- and six-member cyclic products via sequential multi-step aryl-aryl coupling reactions of 2,3,6,7,10,11-hexabromotriphenylene molecules on a Au(111) surface. The final products as well as the organo-gold intermediate structures are identified using scanning tunneling microscopy and density-functional theory simulation. By adjusting reaction temperature and post-annealing temperature, we enhance/suppress the yields of the four-member and six-member cyclic products. We propose an underlying mechanism which is associated with different reaction kinetics of the first-order and second-order reactions. This work exemplifies intricate kinetically-controlled on-surface synthesis when multiple reactions of different reaction order are involved.

Synthesis and characterization of a single-layer conjugated metal-organic structure featuring a non-trivial topological gap.

We employ an on-surface assembly protocol to synthesize a single layer of a two-dimensional conjugated network (Ni3(HITP)2) on a Au(111) surface. The electronic coupling between the π orbital of the diimine ligand and the d orbital of the metal ion renders efficient π-conjugation. Density-functional theory calculations provide evidence of a non-trivial topological gap in the surface-adsorbed single layer. This work demonstrates that single-layer 2D metal-organic frameworks adsorbed on surfaces are a new class of 2D materials that host quantum phases.

Electron Transmission through Coordinating Atoms Embedded in Metal-Organic Nanoporous Networks.

On-surface metal-organic nanoporous networks generally refer to adatom coordinated molecular arrays, which are characterized by the presence of well-defined and regular nanopores. These periodic structures constructed using two types of components confine the surface electrons of the substrate within their nanocavities. However, the confining (or scattering) strength that individual building units exhibit is a priori unknown. Here, we study the modification of the substrate's surface electrons by the interaction with a Cu-coordinated TPyB metal-organic network formed on Cu(111) and disentangle the scattering potentials and confinement properties. By means of STM and angle-resolved photoemission spectroscopy we find almost unperturbed free-electron-like states stemming from the rather weak electron confinement that yields significant coupling between adjacent pores. Electron plane wave expansion simulations match the superlattice induced experimental electronic structure, which features replicating bands and energy renormalization effects. Notably, the electrostatic potential landscape obtained from our ab initio calculations suggests that the molecules are the dominant scattering entities while the coordination metal atoms sandwiched between them act as leaky channels. These metal atom transmission conduits facilitate and enhance the coupling among quantum dots, which are prone to be exploited to engineer the electronic structure of surface electron gases.