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The [ Ph B( t BuIm) 3 ] 1− ligand has gained increased attention since it was first reported in 2006 due to its ability to stabilize highly reactive first row transition metal complexes. In this work, we investigate the coordination chemistry of this ligand with redox-inert zinc to understand how a zinc metal center behaves in such a strong coordinating environment. The Ph B( t BuIm) 3 ZnCl (1) complex can be formed via deprotonation of [ Ph B( t BuIm) 3 ][OTf] 2 followed by the addition of ZnCl 2 . Salt metathesis reaction with nucleophilic n -BuLi yields the highly carbon-rich zinc coordination complex Ph B( t BuIm) 3 ZnBu (2) with three carbene atom donors and one carbanion donor. In contrast, reaction of complex 1 with a less nucleophilic polysulfide reagent, [K.18-C-6] 2 [S 4 ], leads to the formation of a tetrahedral zinc tetrasulfido complex via protonation of one carbene donor to form Ph B( t BuIm) 2 ( t BuImH)Zn(κ 2 -S 4 ) (3).more » « less
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The short C–H⋯S contacts found in available structural data for both small molecules and larger biomolecular systems suggest that such contacts are an often overlooked yet important stabilizing interaction. Moreover, many of these short C–H⋯S contacts meet the definition of a hydrogen bonding interaction. Using available structural data from the Cambridge Structural Database (CSD), as well as selected examples from the literature in which important C–H⋯S contacts may have been overlooked, we highlight the generality of C–H⋯S hydrogen bonding as an important stabilizing interaction. To uncover and establish the generality of these interactions, we compare C–H⋯S contacts with other traditional hydrogen bond donors and acceptors as well as investigate how coordination number and metal bonding affect the preferred geometry of interactions in the solid state. This work establishes that the C–H⋯S bond meets the definition of a hydrogen bond and serves as a guide to identify C–H⋯S hydrogen bonds in diverse systems.more » « less
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Abstract Owing in large part to the advent of integrated biphoton frequency combs, recent years have witnessed increased attention to quantum information processing in the frequency domain for its inherent high dimensionality and entanglement compatible with fiber-optic networks. Quantum state tomography of such states, however, has required complex and precise engineering of active frequency mixing operations, which are difficult to scale. To address these limitations, we propose a solution that employs a pulse shaper and electro-optic phase modulator to perform random operations instead of mixing in a prescribed manner. We successfully verify the entanglement and reconstruct the full density matrix of biphoton frequency combs generated from an on-chip Si 3 N 4 microring resonator in up to an 8 × 8-dimensional two-qudit Hilbert space, the highest dimension to date for frequency bins. More generally, our employed Bayesian statistical model can be tailored to a variety of quantum systems with restricted measurement capabilities, forming an opportunistic tomographic framework that utilizes all available data in an optimal way.more » « less
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Abstract Frequency modulated continuous wave laser ranging (FMCW LiDAR) enables distance mapping with simultaneous position and velocity information, is immune to stray light, can achieve long range, operate in the eye-safe region of 1550 nm and achieve high sensitivity. Despite its advantages, it is compounded by the simultaneous requirement of both narrow linewidth low noise lasers that can be precisely chirped. While integrated silicon-based lasers, compatible with wafer scale manufacturing in large volumes at low cost, have experienced major advances and are now employed on a commercial scale in data centers, and impressive progress has led to integrated lasers with (ultra) narrow sub-100 Hz-level intrinsic linewidth based on optical feedback from photonic circuits, these lasers presently lack fast nonthermal tuning, i.e. frequency agility as required for coherent ranging. Here, we demonstrate a hybrid photonic integrated laser that exhibits very narrow intrinsic linewidth of 25 Hz while offering linear, hysteresis-free, and mode-hop-free-tuning beyond 1 GHz with up to megahertz actuation bandwidth constituting 1.6 × 1015Hz/s tuning speed. Our approach uses foundry-based technologies - ultralow-loss (1 dB/m) Si3N4photonic microresonators, combined with aluminium nitride (AlN) or lead zirconium titanate (PZT) microelectromechanical systems (MEMS) based stress-optic actuation. Electrically driven low-phase-noise lasing is attained by self-injection locking of an Indium Phosphide (InP) laser chip and only limited by fundamental thermo-refractive noise at mid-range offsets. By utilizing difference-drive and apodization of the photonic chip to suppress mechanical vibrations of the chip, a flat actuation response up to 10 MHz is achieved. We leverage this capability to demonstrate a compact coherent LiDAR engine that can generate up to 800 kHz FMCW triangular optical chirp signals, requiring neither any active linearization nor predistortion compensation, and perform a 10 m optical ranging experiment, with a resolution of 12.5 cm. Our results constitute a photonic integrated laser system for scenarios where high compactness, fast frequency actuation, and high spectral purity are required.more » « less
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