Localization of spin and charge in phenalenyl-based neutral radical conductors

We report the development of an experimentally based structural analysis to examine the degree of localization of the spin and charge in the phenalenyl-based neutral radical molecular conductors--the results motivate a reinterpretation of the electronic structure of a number of the radicals that we have reported over the past 10 years. The analysis is based on the well-known relationship between bond order and bond length and makes use of the experimental bond distance deviations between the molecular structure of the radical and its corresponding cation. We determined the single crystal X-ray structure of the ethyl radical (1) at 11 temperatures between 90 K and room temperature so that we could follow the evolution of the structure and the electron density distribution through the magnetic phase transition that occurs in the vicinity of 140 K. We show that the enhanced conductivity in the dimeric ethyl (1) and butyl (3) radicals at the magnetic phase transition results from the development of a complex, but highly delocalized electronic structure and not to the formation of a diamagnetic pi-dimer. We find that the monomeric radicals 4, 12, and 13 have an asymmetric electron density distribution in the crystal lattice whereas radical 11 is the only monomeric radical which remains fully delocalized. The pi-chain radicals (7, 8, 14, and 15) retain the strongly delocalized electronic structures expected for a resonating valence bond ground-state structure.     

Enantioselective organocatalytic Michael addition of aldehydes to nitroethylene: efficient access to gamma2-amino acids

Enantioselective organocatalytic Michael addition of aldehydes to nitroethylene catalyzed by (S)-diphenylprolinol silyl ether provides beta-substituted-delta-nitroalcohols in nearly optically pure form (96-99% ee). The Michael adducts bear a single substituent adjacent to the carbonyl and can be efficiently converted to protected gamma2-amino acids, which are essential for the systematic conformational studies of gamma-peptide foldamers.     

Assembly of silver(I)-organic networks from flexible supramolecular synthons with pendant ethynide arms attached to a naphthyl skeleton

Five new ligands bearing terminal ethynide moieties attached via pendant arms to a naphthyl skeleton have been used in the synthesis of eight silver(I) complexes. In these compounds, the invariable appearance of the mu 4 and mu 5 ligation modes of the ethynide moiety reaffirms the general utility of the silver-ethynide supramolecular synthons R-CC supersetAg n and Ag n subsetCC-R-CC supersetAg n ( n = 4, 5) in coordination network assembly, even when the R group is conformationally flexible. Besides the silver-ethynyl and silver-aromatic interactions, several unconventional intermolecular interactions (argentophilicity, anion-pi, C-H...pi, and CN...pi) also make their appearance.     

Hierarchically Structured Porous Silica Spheres by Microemulsion/Vesicle Templating for Hydrodesulfurization of Fluid Catalytic Cracking Diesel

A series of hierarchically structured porous silica sphere (HSPSS) materials are successfully fabricated by a facile, one‐step microemulsion/vesicle bimodal method in a multicomponent microemulsion system of P123/n‐butanol/1,3,5‐trimethylbenzene/KCl/H₂O (surfactant/cosurfactant/oil/salt/water). The pore structures of the obtained HSPSS products consist of mesocellular foam and mesostructured vesicles. In contrast to the traditional porous silica materials the new structures combine two separate, distinct mesophases with different‐sized mesovoids in a single porous sphere. Moreover, the proportion of every mesophase in obtained HSPSS can be easily adjusted by tuning the initially added amount of n‐butanol or KCl in this multicomponent microemulsion system. When the molar ratio of KCl/tetraethoxysilane is 2.15, the obtained HSPSS material is turned into uniform mesostructured vesicle silica spheres, which consist of many small diameter vesicle particles. The hydrodesulfurization (HDS) activity of fluid catalytic cracking diesel over the HSPSS was tested. HSPSS‐0.75‐1.43 catalyst support with multiple mesoporous structures shows the highest HDS efficiency (98.5%) among all the studied catalysts.     

Fullerene‐Structural Carbon‐Based Dots from C60 Molecules and their Optical Properties

Fullerene‐structural carbon‐based dots (f‐CDs) are synthesized for the first time by chemically oxidizing fullerene molecules (C₆₀) using concentrated HNO₃. The lateral sizes of the f‐CDs distribute in the range of 7–20 nm, and the heights mainly range from 0.4 to 1.3 nm with an average value of 0.7 nm. The presence of massive pentagonal carbon units makes the f‐CDs different from most of graphitic‐CDs in structure and morphology. The f‐CDs exhibit unique luminescent properties such as photoluminescence (PL) and electrochemiluminescence. Based on the investigation of the UV–vis absorption and luminescent properties, a novel and reasonable model is proposed for the PL mechanism of f‐CDs. Furthermore, the obtained f‐CDs show low cytotoxicity and have potential application in cell imaging.     

Proper aspiration level promotes generous behavior in the spatial prisoner’s dilemma game

Zero-determinant strategies, which can unilaterally define a linear relationship between two individuals’ long-term payoff, have drawn much attention to comprehend the emergence of cooperation among individuals with repeated interactions. A subset of zero-determinant strategies, extortion strategy, can let an extortioner’s surplus exceed her opponent’s by a fixed percentage. On the other hand, the dual generosity strategy can ensure that a complier’s payoff is never larger than her opponent’s. In the framework of the prisoner’s dilemma game driven by payoff aspiration, we investigate in this paper the evolution of generosity strategy, in competition with extortion and unconditional defection strategies. We show that extortioners act as a catalyst to induce more defectors to change to compliers. Such influence will enhance when extortioners become more greedy. At a low aspiration level where individuals are easy to be satisfied with their current payoffs, different strategies can coexist. With the increase of aspiration level, unsatisfied individuals are likely to turn to compliers and build long-term reciprocity with their neighbors. However, at a high aspiration level, individuals are difficult to be satisfied with their payoffs and may randomly change their behaviors. Thus proper aspiration level promotes the emergence of generous behavior in the spatial prisoner’s dilemma game.     

Energy-directed tree search: an efficient systematic algorithm for finding the lowest energy conformation of molecules

We present a new systematic algorithm, energy-directed tree search (EDTS), for exploring the conformational space of molecules. The algorithm has been designed to reliably locate the global minimum (or, in the worst case, a structure within 4 kJ mol(-1) of this species) at a fraction of the cost of a full conformational search, and in this way extend the range of chemical systems for which accurate thermochemistry can be studied. The algorithm is inspired by the build-up approach but is performed on the original molecule as a whole, and objectively determines the combinations of torsional angles to optimise using a learning process. The algorithm was tested for a set of 22 large molecules, including open- and closed-shell species, stable structures and transition structures, and neutral and charged species, incorporating a range of functional groups (such as phenyl rings, esters, thioesters and phosphines), and covering polymers, peptides, drugs, and natural products. For most of the species studied the global minimum energy structure was obtained; for the rest the EDTS algorithm found conformations whose total electronic energies are within chemical accuracy from the true global minima. When the conformational space is searched at a resolution of 120 degrees , the cost of the EDTS algorithm (in its worst-case scenario) scales as 2(N) for large N (where N is the number of rotatable bonds), compared with 3(N) for the corresponding systematic search.