Carlos Cordovilla

Luminescent Gold(I) Carbenes from 2-Pyridylisocyanide Complexes: Structural Consequences of Intramolecular versus Intermolecular Hydrogen-Bonding Interactions

Isocyanide [AuX(CNPy-2)] (X = Cl, C6F5, fluoromesityl, 1/2 octafluorobiphenyl) and carbene [AuX{C(NR1R2)(NHPy-2)}] (R1R2NH = primary or secondary amines or 1/2 primary diamine) gold(I) complexes have been synthesized and characterized. For X = Cl, the carbene complexes show aurophilic interactions. The fragment NHPy-2, formed in the carbenes, can give rise to intra- (for primary amines) or intermolecular (for secondary amines) hydrogen bonds, depending on the amine used. These bonds and contacts have been studied in the solid state and in solution. The intermolecular hydrogen bonds are split in an acetone solution, but the intramolecular ones, which close a six-membered ring, survive in solution. Except for the fluoromesityl derivatives, the carbene complexes display luminescent properties.

Liquid-Crystalline Self-Organization of Isocyanide-Containing Dendrimers Induced by Coordination to Gold(I) Fragments

Dendritic polyisocyanides can be considered as promising polytopic ligands to generate a great diversity of metallodendrimers due to the ability of the isocyanide moiety to bind to various transition metals. Here, new isocyanide-containing dendrimers and their corresponding polynuclear gold complexes have been prepared, [G(i)(NC)(Z)] and [G(i)(NCAuR)(Z)], respectively, where G(i) is a poly(phenyl ether) dendrimer, i is the generation number (i = 0, 1, or 2), Z is the number of peripheral groups (Z = 3 x 2(i)), and AuR are the surface groups ([R = Cl, C[triple bond]C-C(6)H(4)-OC(12)H(25), C[triple bond]CC(6)H(2)(OC(12)H(25))(3)]. The compounds are derived from a highly flexible phenyl ether-based dendritic core, G(i), having the general formula G(0) = C(6)H(3)(OC(11)H(22)OC(6)H(4)-)(3), G(1) = C(6)H(3)[OC(11)H(22)OC(6)H(3)(OC(11)H(22)OC(6)H(4)-)(2)](3), G(2) = C(6)H(3)[OC(11)H(22)OC(6)H(3){OC(11)H(22)OC(6)H(3)(OC(11)H(22)OC(6)H(4)-)(2)}(2)](3)), growing from the trivalent phloroglucinol and with undecylene aliphatic spacers between each branching benzene ring and end-functionalized by isocyanide groups. As in their monomeric model counterparts, stable liquid-crystalline phases are induced upon complexation of the AuR gold moieties at the branch termini. The nature of the anionic ligand R promotes the appearance of smectic or columnar mesophases, the formation of which are governed by steric and dipolar interactions. Based on X-ray diffraction experiments, models describing the supramolecular organization of these metallodendrimers into smectic and columnar mesophases are proposed: columnar phases result from the one-dimensional stacking of molecular disks made of self-assembled supermolecules in oblate cylindrical conformation, while the smectic phases form by the lateral two-dimensional registry of the supermolecules in antiparallel head-to-head prolate conformation.

Self‐Organization of Dendritic Supermolecules, Based on Isocyanide–Gold(I), –Copper(I), –Palladium(II), and –Platinum(II) Complexes, into Micellar Cubic Mesophases

First- and second-generation dendrimers with an isocyanide group as the focal functional point (CN-G(n); n: 1,2) and their corresponding organometallic complexes [MCl(CN-G(n))] (M: Au, Cu), [{CuCl(CN-G(n))2}2], and trans-[MI2(CN-G(n))2] (M: Pd, Pt) have been synthesized. The free ligands and the first-generation complexes do not show mesogenic behavior, but all of the second-generation complexes display a thermotropic micellar cubic mesophase, over a large temperature range, and some of them directly at room temperature. The structure of the mesophase consists of the packing of two, discrete polyhedral micellar aggregates in a three-dimensional cubic Im

Gold(I)–carbenes derived from 4-pyridylisocyanide complexes: supramolecular macrocycles supported by hydrogen bonds, and luminescent behavior

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The Stille Reaction, 38 Years Later

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Strain Release in Organic Photonic Nanoparticles for Protease Sensing

Monomeric gold(I) carbenes of the type [AuR[C(NR1R2)(NHPy-4)]] (Py-4 = 4-pyridyl) have been prepared with R = C6F5, Fmes (2,4,6-tris(trifluoromethyl)phenyl) by reaction of the corresponding isocyanide compounds [AuR(CNPy-4)] with primary or secondary amines. The single crystal X-ray diffraction structures of [Au(C6F5)[C(NEt2)(NHPy-4)]].OH2, [Au(Fmes)[C(NEt2)(NHPy-4)]], and [Au(Fmes)[C(NHMe)(NHPy-4)]] show that the presence of the NHPy-4 moiety formed induces the formation of supramolecular macrocycles only supported by hydrogen bond interactions, either with N-H groups of other molecules (tetrameric macrocycles), or with water molecules (dimeric macrocycles). Dimeric gold(I) carbenes were also produced using a diamine to form a bridging carbene, or using octafluorobiphenyl to form a Au-C6F4-C6F4-Au bridge, but the solid state structures of these dimers could not be solved. Most of the complexes herein described display luminescent properties.