Remote gate control of topological transitions in moiré superlattices via cavity vacuum fields.

Placed in cavity resonators with three-dimensionally confined electromagnetic wave, the interaction between quasiparticles in solids can be induced by exchanging virtual cavity photons, which can have a nonlocal characteristic. Here, we investigate the possibility of utilizing this nonlocality to realize the remote control of the topological transition in mesoscopic moiré superlattices at full filling (one electron/hole per supercell) embedded in a split-ring terahertz electromagnetic resonator. We show that gate tuning one moiré superlattice can remotely drive a topological band inversion in another moiré superlattice not in contact but embedded in the same cavity. Our study of remote on/off switching of a topological transition provides a paradigm for the control of material properties via cavity vacuum fields.

Electrophilic aromatic substitution reactions of compounds with Craig-Möbius aromaticity.

Electrophilic aromatic substitution (EAS) reactions are widely regarded as characteristic reactions of aromatic species, but no comparable reaction has been reported for molecules with Craig-Möbius aromaticity. Here, we demonstrate successful EAS reactions of Craig-Möbius aromatics, osmapentalenes, and fused osmapentalenes. The highly reactive nature of osmapentalene makes it susceptible to electrophilic attack by halogens, thus osmapentalene, osmafuran-fused osmapentalene, and osmabenzene-fused osmapentalene can undergo typical EAS reactions. In addition, the selective formation of a series of halogen substituted metalla-aromatics via EAS reactions has revealed an unprecedented approach to otherwise elusive compounds such as the unsaturated cyclic chlorirenium ions. Density functional theory calculations were conducted to study the electronic effect on the regioselectivity of the EAS reactions.

Electron-Photon Chern Number in Cavity-Embedded 2D Moiré Materials.

We explore theoretically how the topological properties of 2D materials can be manipulated by cavity quantum electromagnetic fields for both resonant and off-resonant electron-photon coupling, with a focus on van der Waals moiré superlattices. We investigate an electron-photon topological Chern number for the cavity-dressed energy minibands that is well defined for any degree of hybridization and entanglement of the electron and photon states. While an off-resonant cavity mode can renormalize electronic topological phases that exist without cavity coupling, we show that when the cavity mode is resonant to electronic miniband transitions, new and higher electron-photon Chern numbers can emerge.

Phonon-Limited Valley Polarization in Transition-Metal Dichalcogenides.

The ability to selectively photoexcite at different Brillouin zone valleys forms the basis of valleytronics and other valley-related physics. Symmetry arguments combined with static lattice first-principles calculations suggest an ideal 100% valley polarization in transition-metal dichalcogenides under circularly polarized light. However, experimental reports of the valley polarization range from 32% to almost 100%. Possible explanations for this discrepancy include phonon-mediated transitions, which would place a fundamental limit to valley polarization, and defect-mediated transitions, which could, in principle, be reduced with cleaner samples. We explore the phonon-mediated fundamental limit by performing calculations of phonon-mediated optical absorption for circularly polarized light entirely from the first principles. We also use group theory to reveal the microscopic mechanisms behind the phonon-mediated excitations, discovering contributions from several individual phonon modes and from multiphonon processes. Overall, our calculations show that the phonon-limited valley polarization is around 70% at room temperature for state-of-the-art valleytronic materials including MoSe_{2}, MoS_{2}, WS_{2}, WSe_{2}, and MoTe_{2}. This fundamental limit implies that sufficiently pure transition-metal dichalcogenides are ideal candidates for valleytronics applications.

Heterocyclic Suzuki-Miyaura coupling reaction of metalla-aromatics and mechanistic analysis of site selectivity.

Pd-catalyzed Suzuki-Miyaura cross-coupling is one of the most straightforward and versatile methods for the construction of functionalized arenes and heteroarenes but site-selective cross-coupling of polyhalogenated (hetero)arenes containing identical halogen substituents remains a challenging problem. Herein, we report a new candidate for heterocyclic Suzuki-Miyaura coupling reaction. This candidate has been applied in organometallic systems by combining classical aryl boronic acid reagents with non-classical heteroarenes. Experimental and computational studies of the mechanism of the reactions were performed, with an emphasis on the identity of the reactive species in the oxidative addition step and the nature of the precise site selectivity. The influence of both the aromaticity of the metalla-aromatic substrates and the steric and electronic properties of the halogenated sites are studied in detail.

Magnetic Moments Induced by Atomic Vacancies in Transition Metal Dichalcogenide Flakes.

2D magnetism plays a key role in both fundamental physics and potential device applications. However, the instability of the discovered 2D magnetic materials has been one main obstacle in deep research and potential application of 2D magnetism. Here, a localized magnetic moment induced by Pt vacancies in air-stable type-II Dirac semimetal PtSe2 flakes is reported. The localized magnetic moments give rise to the Kondo effect, evidenced by logarithmic increment of resistance with decreasing temperature and isotropic negative longitudinal magnetoresistance. Additionally, the induced magnetic moment and Kondo temperature appear to depend on thickness in the thinner samples (<10 nm). The small magnetocrystalline anisotropy revealed by first-principles calculation indicates that the magnetic moments are randomly localized instead of long-range ordered. The findings demonstrate a new means to induce magnetism in 2D non-magnetic materials.

Tuning Charge Carrier and Spin Transport Properties via Structural Modification of Polymer Semiconductors.

Targeted design of organic semiconductors in organic spintronics is relatively limited. Therefore, four conjugated polymers with analogous structures based on isoindigo (IID) units were designed and synthesized to investigate the structure-property relationships in spin and charge carrier transport. Structural design strategies include introduction of pyridinic nitrogen atoms into IID units to change electronic structures and alteration of different branching points of alkyl chains to adjust the aggregation structure. By fabricating polymer field-effect transistors (PFETs) and organic spin valves (OSVs), all of the polymers exhibited good ambipolar field-effect properties (all of the mobilities exceeding 0.3 cm2 V-1 s-1) and relatively high magnetoresistance (MR) values (maximum up to 25%). Most importantly, it is found that the introduction of pyridinic nitrogen into the IID units can improve MR values of OSVs and electron mobilities of PFETs, whereas the extension of alkyl chain branching points can reduce MR values of the conjugated polymers. This work is the first attempt to thoroughly study the structure-property relationship in the OSVs, combined with molecular design of the conjugated polymers, which provides a guideline for molecular engineering, especially for organic spintronics.

Well-Balanced Ambipolar Conjugated Polymers Featuring Mild Glass Transition Temperatures Toward High-Performance Flexible Field-Effect Transistors.

Conjugated polymers, which can be fabricated by simple processing techniques and possess excellent electrical performance, are key to the fabrication of flexible polymer field-effect transistors (PFETs) and integrated circuits. Herein, two ambipolar conjugated polymers based on (3E,7E)-3,7-bis(2-oxo-1H-pyrrolo[2,3-b]pyridin-3(2H)-ylidene)benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione and dithienylbenzothiadiazole units, namely PNBDOPV-DTBT and PNBDOPV-DTF2BT, are developed. Both copolymers possess almost planar conjugated backbone conformations and suitable highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energy levels (-5.64/-4.38 eV for PNBDOPV-DTBT and -5.79/-4.48 eV for PNBDOPV-DTF2BT). Note that PNBDOPV-DTBT has a glass transition temperature (140 °C) lower than the deformation temperature of polyethylene terephthalate (PET), meaning well-ordered molecular packing can be obtained on PET substrate before its deformation in mild thermal annealing process. Flexible PFETs based on PNBDOPV-DTBT fabricated on PET substrates exhibit high and well-balanced hole/electron mobilities of 4.68/4.72 cm2 V-1 s-1 under ambient conditions. After the further modification of Au source/drain electrodes with 1-octanethiol self-assembled monolayers, impressively high and well-balanced hole/electron mobilities up to 5.97/7.07 cm2 V-1 s-1 are achieved in the flexible PFETs. Meanwhile, flexible complementary-like inverters based on PNBDOPV-DTBT on PET substrate also afford a much high gain of 148. The device performances of both the PFETs and inverters are among the highest values for ambipolar conjugated polymers reported to date.