Synthesis and optoelectronic properties of new ethynylated pyrazine derivatives

Several diaryleneethynylpyrazine derivatives, in which the pyrazine unit is electron-deficient, have been synthesised using Sonogashira palladium-catalysed cross-coupling reactions. Compound 32, an important intermediate in the synthesis of diaryleneethynylpyrazine derivatives was made by a modified literature procedure which improved the yield. Examination of optical absorption and photoluminescence spectra of compound 37 shows that the pyrazine unit does not change the behaviour significantly compared to analogue 42, while compound 38 shows pyridine substituents have a profound effect on the photophysics of these pyrazine systems. The redox properties of representative compound 37 were studied by cyclic voltammetry, which shows that reduction of 37 to its radical anion occurs as a reversible process at high negative potentials of ca. -1.87 V. The X-ray crystal structure of 37 is also presented. Quantum mechanical calculations of the geometry and electronic structure were performed for compound 37; the known phenylene analogue 42 was calculated at the same level for comparison. The results show that the energies of both HOMO and LUMO orbitals of 37 are decreased compared to 42. The calculated value of the HOMO-LUMO gap of 37 (3.56 eV) is close to that estimated from the red edge of the longest wavelength absorption (382 nm = 3.25 eV)

Nonconvex Generalization of ADMM for Nonlinear Equality Constrained Problems

The ever-increasing demand for efficient and distributed optimization algorithms for large-scale data has led to the growing popularity of the Alternating Direction Method of Multipliers (ADMM). However, although the use of ADMM to solve linear equality constrained problems is well understood, we lacks a generic framework for solving problems with nonlinear equality constraints, which are common in practical applications (e.g., spherical constraints). To address this problem, we are proposing a new generic ADMM framework for handling nonlinear equality constraints, neADMM. After introducing the generalized problem formulation and the neADMM algorithm, the convergence properties of neADMM are discussed, along with its sublinear convergence rate $o(1/k)$, where $k$ is the number of iterations. Next, two important applications of neADMM are considered and the paper concludes by describing extensive experiments on several synthetic and real-world datasets to demonstrate the convergence and effectiveness of neADMM compared to existing state-of-the-art methods

Joint Syntacto-Discourse Parsing and the Syntacto-Discourse Treebank

Discourse parsing has long been treated as a stand-alone problem independent from constituency or dependency parsing. Most attempts at this problem are pipelined rather than end-to-end, sophisticated, and not self-contained: they assume gold-standard text segmentations (Elementary Discourse Units), and use external parsers for syntactic features. In this paper we propose the first end-to-end discourse parser that jointly parses in both syntax and discourse levels, as well as the first syntacto-discourse treebank by integrating the Penn Treebank with the RST Treebank. Built upon our recent span-based constituency parser, this joint syntacto-discourse parser requires no preprocessing whatsoever (such as segmentation or feature extraction), achieves the state-of-the-art end-to-end discourse parsing accuracy.Comment: Accepted at EMNLP 201