▪ Abstract Recently, sum frequency generation (SFG) vibrational spectroscopy has been developed into a powerful technique to study surfaces of polymer materials. This review summarizes the significant achievements in understanding surface molecular chemical structures of polymer materials obtained by SFG. It reviews in situ detection at the molecular level of surface structures of some common polymers in air, surface segregation of small end groups, polymer surface restructuring in water, and step-wise changed polymer blend surfaces. Studies of surface glass transition and surface structures modified by rubbing, plasma deposition, UV light irradiation, oxygen ion and radical irradiation, and wet etching are also discussed. SFG probing of polymer surfaces provides valuable insights into the relations between polymer surface structures and surface properties, which will assist in the design of polymer materials with desired surface properties.
Recent theoretical studies inspired by experiments on the Kitaev magnet $α$-RuCl$_3$ highlight the nontrivial impact of phonons on the thermal Hall conductivity of chiral topological phases. Here we introduce mixed mesoscopic-macroscopic devices that allow refined thermal-transport probes of non-Abelian spin liquids with Ising topological order. These devices feature a quantum-coherent mesoscopic region with negligible phonon conductance, flanked by macroscopic lobes that facilitate efficient thermalization between chiral Majorana edge modes and bulk phonons. We show that our devices enable $(i)$ accurate determination of the quantized thermal Hall conductivity, $(ii)$ identification of non-Abelian Ising anyons via the temperature dependence of the thermal conductance, and most interestingly $(iii)$ single-anyon detection through heat-based anyon interferometry. Analogous results apply broadly to phonon-coupled chiral topological orders.
The reactive complex (NSiN)Ir(H)(OTf)(coe) (1; NSiN = bis(8-quinolyl)methylsilyl, coe = cyclooctene) was generated by reaction of the previously reported (NSiN)Ir(H)Cl(coe) with 1 equiv of AgOTf. Addition of Ph3SiH to 1 in benzene led to Si−H bond activation and octane elimination with formation of the α-Ph-migrated, 16-electron product (NSiN)IrPh(SiPh2OTf) (2). The 29Si{1H} NMR resonance of 2 at δ 54.0 indicates iridium silyl character, and X-ray crystallography reveals the presence of a highly distorted triflatosilyl group. In acetonitrile, 1 reacts with various silanes to give stable, cationic Ir(III) complexes of the type [(NSiN)IrSiR3(NCMe)2][OTf] (R = OSiMe3, Et, Ph) or [(NSiN)Ir{SiH(R)Ph}(NCMe)2][OTf] (R = H, Ph) in good yields. Complex 1 is an active catalyst for arylsilane redistribution and for the dehydrogenative silylation of arenes. The cationic, THF complex [(NSiN)Ir(H)(coe)(THF)][B(C6F5)4] (10), a product of the reaction of 1 with 1 equiv of Li(Et2O)3[B(C6F5)4] in THF, is a slower catalyst for silane redistribution and dehydrogenative arene silylation. A series of new iridium phosphine complexes were prepared, including (NSiN)Ir(H)Cl(PMe3) (13), [(κ2-NSiN)Ir(H)(PMe3)3][Cl] (14), and (κ1-NSiN)Ir(H)(Me)(PMe3)3 (15). Treatment of the previously prepared (NSiN)Ir(H)Cl(PPh3) with 1 equiv of LiBEt3H afforded the dihydride complex (NSiN)IrH2(PPh3) (11), which features a hydride ligand in a coordination site trans to the NSiN silyl group. The triflate complex (NSiN)Ir(H)(OTf)(PPh3) (16) was obtained by reaction of (NSiN)Ir(H)Cl(PPh3) with 1 equiv of AgOTf in dichloromethane or by reaction of 1 with 1 equiv of PPh3 in dichloromethane.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
During the past decade, the use of Au(I) complexes for the catalytic activation of C-C π-bonds has been investigated intensely. Over this time period, the development of homogeneous gold catalysis has been extraordinarily rapid and has yielded a host of mild and selective methods for the formation of carbon-carbon and carbon-heteroatom bonds. The facile formation of new bonds facilitated by gold naturally led to efforts toward rendering these transformations enantioselective. In this Account, we survey the development of catalysts and ligands for enantioselective gold catalysis by our research group as well as related work by others. We also discuss some of our strategies to address the challenges of enantioselective gold(I) catalysis. Early on, our work with enantioselective gold-catalyzed transformations focused on bis(phosphinegold) complexes derived from axially chiral scaffolds. Although these complexes were highly successful in some reactions like cyclopropanation, the careful choice of the weakly coordinating ligand (or counterion) was necessary to obtain high levels of enantioselectivity for the case of allene hydroamination. These counterion effects led us to use the anion itself as a source of chirality, which was successful in the case of allene hydroalkoxylation. In general, these tactics enhance the steric influence around the reactive gold center beyond the two-coordinate ligand environment. The use of binuclear complexes allowed us to use the second gold center and its associated ligand (or counterion) to exert a further steric influence. In a similar vein, we employed a chiral anion (in place of or in addition to a chiral ligand) to move the chiral information closer to the reactive center. In order to expand the scope of reactions amenable to enantioselective gold catalysis to cycloadditions and other carbocyclization processes, we also developed a new class of mononuclear phosphite and phosphoramidite ligands to supplement the previously widely utilized phosphines. However, we needed to judiciously design the steric environment to create "walls" that enclose the gold center. We also successfully applied these same considerations to the development of binuclear carbene ligands for gold. Finally, we describe the design of bifunctional urea-monophosphine ligands used in a gold-catalyzed three-component coupling.
Abstract : The Ethane architecture, developed at Stanford University, demonstrated that a novel approach to building secure networks could support superior low-level security and flexible policy-based control over individual flows. However, Ethane only provided operators with a single function: policy-based access control. Moreover, Ethane's policy was expressed in a language that did not have a rigorous logical foundation. Almost a year of subsequent work, reported on here, extended Ethane to address these two shortcomings. First, the Ethane architecture was evolved from Ethane's narrowly targeted design to a fully general network operating system called NOX, which provides users with full-blown programmatic interface. Second, the policy language has evolved from the Ethane's primitive pol-eth to a much more powerful and rigorously analyzed Flow-Based Security Language (FSL). This report describes these two advances.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.