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Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging as a unique class of 2D electronic materials. However, intrinsically semiconducting 2D c-MOFs with gaps in the Vis-NIR and high charge carrier mobility have been rare. Most of the reported semiconducting 2D c-MOFs are metallic (i.e. gapless), which limits their use in applications where larger band gaps are needed for logic devices. Herein, we design a new D2h-geometric ligand, 2,3,6,7,11,12,15,16-octahydroxyphenanthro(9,10b)triphenylene (OHPTP), and synthesize the first example of a 2D c-MOF single crystal (OHPTP-Cu) with a rhombohedral pore geometry after coordination with copper. The continuous rotation electron diffraction (cRED) analysis unveils the orthorhombic crystal structure at the atomic level with a unique AB layer stacking. The resultant Cu2(OHPTP) is a p-type semiconductor with an indirect band gap of about 0.50 eV and exhibits high electrical conductivity of 0.10 S cm-1 and high charge carrier mobility of 10.0 cm2V-1s-1. Density-functional theory calculations underline the predominant role of the out-of-plane charge transport in this semiquinone-based 2D c-MOFs., Comment: 11 pages 5 figures

The air-water interface is a highly prevalent phase boundary with a far-reaching impact on natural and industrial processes. Water molecules behave differently at the interface compared to the bulk, exhibiting anisotropic orientational distributions, reduced intermolecular connectivity in the hydrogen bond network, and significantly slower dynamics. Despite many decades of research, the thickness of the structural anisotropy in the interfacial layer remains controversial, with a direct experimental measurement being absent. In this study, we utilise an advancement in non-linear vibrational spectroscopy to gain access to this important parameter. Combining phase-resolved sum- and difference-frequency generation (SFG and DFG) responses, we directly measure the decay in structural anisotropy of the air-water interface. We find a decay length of ~6-8\r{A}, in excellent agreement with depth-resolved SFG spectra calculated from ab initio parameterised molecular dynamics (MD) simulations. The result reveals surprisingly short anisotropic orientational correlations from the interfacial layer that are even shorter than in the bulk. Furthermore, the recorded SFG and DFG responses are decomposed into a vibrationally resonant and non-resonant contribution through isotopic exchange measurements. Through their separate analysis, we show that the resonant response is a sensitive probe of the structural anisotropy at the interface whereas the non-resonant contribution contains a significant isotropic contribution from the bulk and therefore only partially reports on the interfacial structure. This finding places stringent restrictions on the insight available through both purely non-resonant and second-order intensity studies., Comment: 18 pages, 4 figures, 1 table, supplementary information

We report electro-optic sampling (EOS) response and terahertz (THz) optical rectification (OR) in z-cut alpha-quartz. Due to its small effective second-order nonlinearity, echo-free waveform of intense THz pulses with a few MV/cm electric-field strength can be measured faithfully with no saturation effect. Both its OR and EOS responses are broad with extension up to ~8 THz. Strikingly, the latter responses are independent of the crystal thickness, a plausible indication of strong surface contribution to the total second-order nonlinear susceptibility of quartz. Our study introduces thin quartz plates as the reliable THz electro-optic medium for echo-free, high field THz detection.