Design and Synthesis of Bicyclo[4.3.0]nonene Nucleoside Analogues.

Nucleoside analogues are effective antiviral agents, and the continuous emergence of pathogenic viruses demands the development of novel and structurally diverse analogues. Here, we present the design and synthesis of novel nucleoside analogues with a carbobicyclic core, which mimics the conformation of natural ribonucleosides. Employing a divergent synthetic route featuring an intermolecular Diels-Alder reaction, we successfully synthesized carbobicyclic nucleoside analogues with high antiviral efficacy against respiratory syncytial virus.

π-Stacking Stopper-Macrocycle Stabilized Dynamically Interlocked [2]Rotaxanes.

The synthesis of mechanically interlocked molecules is valuable due to their unique topologies. With π-stacking intercomponent interaction, e.g.

Assembly of high-symmetry silver(i) alkyl-1,3-diynyl cluster complexes via core transformation.

New tetranuclear supramolecular precursors [(R-C[triple bond, length as m-dash]C-C[triple bond, length as m-dash]C)Ag(PPh)] (R = iPr and chx) are employed to construct three polynuclear silver(i) alkyl-1,3-diynyl cluster complexes (1-3) that bear the same novel trigonal bipyramidal Ag core consolidated by silver-ethynide and argentophilic interactions. The present results strongly suggest that the assembly of high-symmetry medium-nuclearity clusters 1-3 is initiated by the accretion of additional Ag(i) ions by the Ag template of the precursors through argentophilic (<3.4 Å) interaction, and demonstrate that core transformation is an effective synthetic route to high-symmetry metal clusters.

Assembly of Heterometallic Silver(I)-Copper(I) Alkyl-1,3-diynyl Clusters via Inner-Core Expansion.

New tetranuclear supramolecular precursors [(R-C≡C-C≡C)Ag] (R = Pr, Bu, and chx) are employed to construct a series of heterometallic silver(I)-copper(I) alkyl-1,3-diynyl cluster complexes (1-9) that bear a common CuAg core (normally trigonal-planar, but can be distorted to pyramidal) consolidated by cupro-argentophilic interaction under 3.12 Å, as found in 1 and 2. The photophysical properties of the multinuclear supramolecular precursors and selected complexes have been investigated.

Organosilver(I) framework assembly with trifluoroacetate and enediyne-functionalized alicycles.

Eight new silver(I) trifluoroacetate complexes based on a series of designed ligands, each featuring an alicyclic ring with enediyne functionality, have been synthesized and characterized by single-crystal X-ray diffraction. Each ethynide terminal is inserted into an Agn (n = 4-5) basket, leading to the generation of coordination chain or layer structures, but the well shielded ethenyl group does not take part in silver-olefin bonding. Variation in ring size of the alicycles is shown to influence the construction of the organosilver(I) coordination networks, which are consolidated by weak intermolecular interactions in the crystal structures.

Synthesis of unstable carbides Ag2C(2n) (n = 3, 4) and characterization via crystallographic analysis of their double salts with silver(I) trifluoroacetate.

Two new silver(I) carbides, Ag2C6 and Ag2C8, have been synthesized, and single-crystal X-ray analysis of their crystalline silver(I) trifluoroacetate complexes, Ag2C6·8AgCF3CO2·6H2O, 4(Ag2C6)·16AgCF3CO2·14.5DMSO, and 2.5(Ag2C8)·10AgCF3CO2·10DMSO, provides detailed information on the influence of ligand disposition and orientation of the all-carbon anionic ligands in the construction of multidimensional supramolecular structures, which are consolidated by argentophilic and weak inter-/intramolecular interactions.

Systematic investigation of silver-carbon bonding in coordination frameworks with aryl ligands that contain ethynyl and ethenyl substituents.

Single-crystal X-ray diffraction of a series of ten crystalline silver(I)-trifluoroacetate complexes that contained designed ligands, each of which was composed of an aromatic system that was functionalized with terminal and internal ethynyl groups and a vinyl substituent, provided detailed information on the influence of ligand disposition and orientation, coordination preferences, and the co-existence of different types of silver(I)-carbon bonding interactions (silver-ethynide, silver-ethynyl, silver-ethenyl, and silver-aromatic) on the construction of coordination networks that were consolidated by argentophilic and weak inter/intramolecular interactions. The complex AgL10⋅6 AgCF3CO2⋅H2O⋅ MeOH (HL10 = 1-{[4-(prop-2-ynyloxy)-3-vinylphenyl]ethynyl}naphthalene) is the first reported example that exhibits all four kinds of silver(I)-carbon bonding interactions in the solid state.

Enlargement of globular silver alkynide cluster via core transformation.

The multinuclear metal-ligand supramolecular synthon R-C≡C⊃Ag(n) (R = alkyl, cycloalkyl; n = 3, 4, 5) has been employed to construct two high-nuclearity silver ethynide cluster compounds, [Cl(6)Ag(8)@Ag(30)((t)BuC≡C)(20)(ClO(4))(12)]·Et(2)O (1) and [Cl(6)Ag(8)@Ag(30)(chxC≡C)(20)(ClO(4))(10)](ClO(4))(2)·1.5Et(2)O (chx = cyclohexyl) (2), that bear the same novel Cl(6)Ag(8) central core. The synthesis of 1 made use of [Cl@Ag(14)((t)BuC≡C)(12)]OH as a precursor, and its reaction with AgClO(4) in CH(2)Cl(2) resulted in an increase in nuclearity from 14 to 38.