Fluorinated tris(pyridyl)borate ligand support on coinage metals

A useful ligand involving three pyridyl donor arms and fluorocarbon substituents surrounding the coordination pocket has been assembled and utilized in coinage metal chemistry. This tris(pyridyl)borate serves as an excellent...

Synthesis and coordination to the coinage metals of a trimethylpyrazolyl substituted 3-arylacetylacetone

The ligand 3-(4-(1,3,5-trimethyl-1H-pyrazol-4-yl)phenyl)acetylacetone (1) combines a Pearson hard O,O′ chelating acetylacetone donor with a softer pyrazole N donor bridged by a phenylene spacer. Deprotonation and coordination to CuII leads to a square planar bis-acetylacetonato complex; interpreting the close proximity of an adjacent complex’s pyrazole moiety as an η 2 ${{\eta}}^{2}$ coordination to the axial CuII position leads to a two dimensional extended structure. The N donor capabilities are proven by coordination to AgPF6 and AuCl; for AgI a cationic linear bis-pyrazole complex as a toluene solvate is obtained with toluene-pyrazole π-interactions and an essentially uncoordinated PF 6 - ${{\mathrm{PF}}_{6}}^{-}$ anion. In the case of AuCl a neutral linear coordination compound with one chlorido and one pyrazole ligand 1 is obtained. Comparing the dihedral angles with a closely related but shorter ligand reveals a larger rotational degree of freedom in 1, allowing for richer architectures in emerging coordination polymers.

Methods to Generate Structurally Hierarchical Architectures in Nanoporous Coinage Metals

The fundamental essence of material design towards creating functional materials lies in bringing together the competing aspects of a large specific surface area and rapid transport pathways. The generation of structural hierarchy on distinct and well-defined length scales has successfully solved many problems in porous materials. Important applications of these hierarchical materials in the fields of catalysis and electrochemistry are briefly discussed. This review summarizes the recent advances in the strategies to create a hierarchical bicontinuous morphology in porous metals, focusing mainly on the hierarchical architectures in nanoporous gold. Starting from the traditional dealloying method and subsequently moving to other non-traditional top-down and bottom-up manufacturing processes including templating, 3D printing, and electrodeposition, this review will thoroughly examine the chemistry of creating hierarchical nanoporous gold and other coinage metals. Finally, we conclude with a discussion about the future opportunities for the advancement in the methodologies to create bimodal structures with enhanced sensitivity.