A Rock‐Salt‐Like Lattice Structure Consisting of Monocationic and Monoanionic Au^IAg^ICu^II Supramolecular Cages of D‐Penicillaminate

Abstract

Over the past decade, considerable interest has been devoted to the controlled synthesis of metallosupramolecular species, such as finite coordination rings and cages and infinite coordination polymers, not only because of their intriguing structural diversity but also because of their potential as new functional materials.[1] While the most common approach to obtain metallosupramolecules is based on the self-assembly of multidentate organic ligands and metal ions, our synthetic strategy has been directed toward the use of metal complexes with sulfur-containing aminocarboxylates such as l-cysteinate (l-cys) and d-penicillaminate (d-pen) as building blocks, which are aggregated by forming S-bridged structures with transition metal ions.[2] Recently, we have found that the sixcoordinate complexes [Co(l-À can bind to Ag I ions not only through thiolato groups but also through pendant carboxylate groups to produce a variety of supramolecular structures, including 1D helix and 2D sheet. [2b-d] This result showed the suitability of l-cys and d-pen metal complexes as favorable building blocks that adopt various binding modes toward transition metal ions.To expand the range of mixed-metal supramolecular architectures constructed from simple sulfur-containing aminocarboxylates, we investigated the binding ability of the twocoordinate Au I complex [Au(d-pen-S) 2 ] 3À , [3] which was prepared as a model of gold-based antiarthritis drugs. In this complex, two d-pen ligands coordinate to a linear Au I center only through thiolato groups, thus leaving two amino and two carboxylate groups as potential binding sites for additional metal ions, besides two coordinated thiolato groups. Here we report that the stepwise reaction of [Au(d-pen-S)

The Coordination and Supramolecular Chemistry of Gold Metalloligands

“…The reactiono f83 with CuCl 2 followed by crystallization gave rise to as alt containing the three coinage metal atoms, which is composed of large monocationic and monoanionic cages containing 20 and 21 metal atoms, respectively.T hese cages are arranged in as upramolecular ionic structure resembling that of the rock salt. [72] Te tranuclear complexes containing two square-planar centers have been isolated by reactiono fH 2 [80]w ith Ni II , [73] Pd II [74] or Pt II [74] salts (Figure 25). The cis,cis or trans,trans forms of these complexes (84 and 85)h ave been isolated as potassium salts.…”

Tetrapotassium [μ2-N-carboxylato-D-penicillaminato(3–)-5:6κ2S:S][μ2-D-penicillaminato(1–)-2:3κ2S:S]tetrakis[μ2-D-penicillaminato(2–)]-1:2κ3N,S:S;1:6κ3N,S:S;3:4κ3S:N,S;4:5κ3N,S:S-2,3,5,6-tetragold(I)-1,4-dinickel(II) ethanol monosolvate decahydrate

“…While studying the reactivity of the 3-mercapto derivative of valine (d-penicillamine or d-H 2 pen) bound to a gold(I) centre towards various metal ions (Toyota et al, 2005;Taguchi et al, 2007), we found that red crystals containing Au I and Ni II atoms in a 2:1 ratio are formed when a solution containing [Au(d-pen) 2 ] 3and Ni 2+ was allowed to stand in a refrigerator for two months. We report herein the crystal structure of (I) containing a d-carbaminopenicillaminate (d-cp) ligand that bridges two Au I atoms through a thiolate group.…”

Gold–Heterometal Interactions and Bonds

“…Finally, the affinity of coinage metals for sulfur ligands was recently used to create a unique metallosupramolecular architecture containing Au(I), Ag(I) and Cu(II) in the same metal frameworks [628]. Thus, the reaction of (NH 4 )[Au(D-Hpen) 2 ] with AgNO 3 (1 : 1 molar ratio), followed by treatment with excess of CuCl 2 , afforded the isolation of blue crystals of a heterometallic aggregate with a rock-salt-like lattice structure.…”