Ancillary Ligands and Spectator Cations as Controlling Factors in the Construction of Coordination and Hydrogen‐Bonded Networks with the tert‐Bu‐CC⊃Ag_n (n=4, 5) Supramolecular Synthon

Abstract

Supramolecular networks constructed with the tBu--C[triple bond]C superset Ag(n) (n=4 or 5) metal-ligand synthon and trifluoroacetate have been transformed through the introduction of ancillary terminal nitrile ligands, from acetonitrile through propionitrile to tert-butyronitrile, giving rise to a 2D coordination network in AgC[triple chemical bond]CtBu3 AgCF(3)CO(2)H(2)O (1), a 2D hydrogen-bonded network in AgC[triple chemical bond]CtBu5 AgCF(3)CO(2)4 CH(3)CNH(2)O (2), a 2D hybrid coordination/hydrogen-bonded network in AgC[triple chemical bond]CtBu3 AgCF(3)CO(2)CH(3)CH(2)CN2 H(2)O (3), and another 2D coordination network in AgC[triple chemical bond]CtBu4 AgCF(3)CO(2) (CH(3))(3)CCN2 H(2)O (4). Concomitantly, the linkage modes between adjacent ethynide-bound Ag(n) aggregates in these compounds are also changed. A layer-type hydrogen-bonded host lattice in isostructural AgC[triple chemical bond]CtBu4 AgCF(3)CO(2)(R(4)N)(CF(3)CO(2)) 2 H(2)O (R(4)=BnMe(3), 5; R(4)=Et(4), 6; R(4)=nPr(4), 7) is obtained by introducing quaternary ammonium cations as guest templates, which occupy the interstices and thereby mediate the interlayer separation. Use of the bulky nBu(4)N(+) cation leads to disruption of the host network in AgC[triple bond]CtBu4 AgCF(3)CO(2)3[(nBu(4)N)(CF(3)CO(2))]H(2)O (8) with generation of a discrete dense nido-Ag(5) cluster.

Investigation of the Effect of a Mixed-Ligand on the Accommodation of a Templating Molecule into the Structure of High-Nucleus Silver Clusters

“…(AgCC t Bu) n and (AgCCisopropyl) n were synthesized according to the literature. 33 t BuC CH, isopropyl-CCH, and Ag 2 O were purchased from Shanghai ALADDIN Co., Ltd. All other reagents were commercially available and were used as received without further purification. The FT-IR spectra were performed by KBr pellets in the range 4000400 cm −1 by using a WQF-520A FT-IR spectrometer.…”

A silver-alkynyl cluster encapsulating a fluorescent polyoxometalate core: enhanced emission and fluorescence modulation

“…21 [ t BuCuCAg] n was synthesized according to the literature. 22 FTIR spectra were recorded in the 500-2500 cm −1 region on an Alpha Centauri FT/IR spectrophotometer (KBr pellets). Elemental analyses for C and H were performed on a Perkin-Elmer 240C analyzer.…”

Threefold Collaborative Stabilization of Ag14‐Nanorods by Hydrophobic Ti16‐Oxo Clusters and Alkynes: Designable Assembly and Solid‐State Optical‐Limiting Application

“…Based on the above structural analysis, the Ti 8 and Ag 5 units are the basic building blocks for the construction of Ti 8 , Ag 5 @Ti 8 and Ag 14 @Ti 16 . Considering the closely related structural evolution from Ti 8 to Ag 14 @Ti 16 and their correlated synthetic conditions, we can propose a formation mechanism of the Ag 14 @Ti 16 clusters as following (Scheme 2): firstly, AgAc would aggregate to form a {Ag 5 } in the presence of alkyne and R‐COOH as indicated by the previous reported Ag 5 clusters isolated in similar synthetic condition by Thomas C. W. Mak; [37] meanwhile, Ti(O i Pr) 4 could assemble with R‐COOH ligands to produce Ti 8 moieties quickly; then the assembled Ti 8 moieties captured Ag 5 to form the Ag 5 @Ti 8 intermediates; finally, such two Ag 5 @Ti 8 intermediates further sandwiched four Ag ions and aggregated into the Ag 14 @Ti 16 clusters.…”