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81.
Jiawang Zhou Ljiljana Stojanovi Andrey A. Berezin Tommaso Battisti Abigail Gill Benson M. Kariuki Davide Bonifazi Rachel Crespo-Otero Michael R. Wasielewski Yi-Lin Wu 《Chemical science》2021,12(2):767
Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.The number and position of halogen substituents in purely organic π–π* chromophores critically affect the efficiency of phosphorescence. 相似文献
82.
Jordan De Jesus Silva Niccolò Bartalucci Benson Jelier Samantha Grosslight Tobias Gensch Claas Schünemann Bernd Müller Paul C. J. Kamer Christophe Copéret Matthew S. Sigman Antonio Togni 《Helvetica chimica acta》2021,104(12):e2100200
A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts. 相似文献
83.
Dr. Tian Qin Dr. Lara R. Malins Jacob T. Edwards Rohan R. Merchant Alexander J. E. Novak Jacob Z. Zhong Riley B. Mills Ming Yan Dr. Changxia Yuan Dr. Martin D. Eastgate Prof. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2017,56(1):260-265
Two named reactions of fundamental importance and paramount utility in organic synthesis have been reinvestigated, the Barton decarboxylation and Giese radical conjugate addition. N ‐hydroxyphthalimide (NHPI) based redox‐active esters were found to be convenient starting materials for simple, thermal, Ni‐catalyzed radical formation and subsequent trapping with either a hydrogen atom source (PhSiH3) or an electron‐deficient olefin. These reactions feature operational simplicity, inexpensive reagents, and enhanced scope as evidenced by examples in the realm of peptide chemistry. 相似文献
84.
Phil Hanlon 《Proceedings of the American Mathematical Society》2008,136(11):3741-3749
Let be a simple graph with nodes. The coloring complex of , as defined by Steingrimsson, has -faces consisting of all ordered set partitions, in which at least one contains an edge of . Jonsson proved that the homology of the coloring complex is concentrated in the top degree. In addition, Jonsson showed that the dimension of the top homology is one less than the number of acyclic orientations of .
In this paper, we show that the Eulerian idempotents give a decomposition of the top homology of into components . We go on to prove that the dimensions of the Hodge pieces of the homology are equal to the absolute values of the coefficients of the chromatic polynomial of . Specifically, if we write , then .
85.
In this paper, we present a primal-dual interior-point method for solving nonlinear programming problems. It employs a Levenberg-Marquardt (LM) perturbation to the Karush-Kuhn-Tucker (KKT) matrix to handle indefinite Hessians and a line search to obtain sufficient descent at each iteration. We show that the LM perturbation is equivalent to replacing the Newton step by a cubic regularization step with an appropriately chosen regularization parameter. This equivalence allows us to use the favorable theoretical results of Griewank (The modification of Newton’s method for unconstrained optimization by bounding cubic terms, 1981), Nesterov and Polyak (Math. Program., Ser. A 108:177–205, 2006), Cartis et al. (Math. Program., Ser. A 127:245–295, 2011; Math. Program., Ser. A 130:295–319, 2011), but its application at every iteration of the algorithm, as proposed by these papers, is computationally expensive. We propose a hybrid method: use a Newton direction with a line search on iterations with positive definite Hessians and a cubic step, found using a sufficiently large LM perturbation to guarantee a steplength of 1, otherwise. Numerical results are provided on a large library of problems to illustrate the robustness and efficiency of the proposed approach on both unconstrained and constrained problems. 相似文献
86.
We study new posets Q obtained by removing from a geometric lattice L ofa biased graph certain flats indexed by a simplicial complex
. (One example of L is the lattice of flats of thevector matroid of a root system B
n
.) We study the structureand compute the characteristic polynomial of Q. With certainchoices of L and
, including ones for which Q is alattice interpolating between those of B
n
and D
n
, we observe curious relationships among the roots of thecharacteristic polynomials of Q, L, and
. 相似文献
87.
88.
H. P. Benson 《Journal of Optimization Theory and Applications》1982,38(3):341-361
In this paper, we present several new properties of the admissible points of a convex polyhedron. These properties can be classified into two categories. One category concerns the characterization and generation of these points. The other category concerns the circumstances under which these points are efficient solutions for linear multiple-objective programs with nonnegative criteria matrices. To illustrate some of the potential utility of these properties, we describe their application to two practical problems. These problems are the linear multiple-objective problem with interval coefficients and the problem of optimizing over the efficient set.This research was supported, in part, by the Center for Econometrics and Decision Sciences, University of Florida, Gainesville, Florida. 相似文献
89.
David John Benson 《Archiv der Mathematik》2017,109(5):413-414
Let K be a field of characteristic zero, and let R be a ring containing K. Then either \(R^\times = K^\times \) or \(K^\times \) is a subgroup of infinite index in \(R^\times \). 相似文献
90.