Treatment of (NH4)[Au(D‐Hpen‐S)2](D‐H2pen = D‐penicillamine) with CoCl2·6H2O in an acetate buffer solution, followed by air oxidation, gave neutral AuICoIII and anionic AuI3CoIII2 polynuclear complexes, [Au3Co3(D‐pen‐N,O,S)6]([1]) and [Au3Co2(D‐pen‐N,S)6]3− ([2]3−), which were separated by anion‐exchange column chromatography. Complexes [1] and [2]3− each formed a single isomer, and their structures were determined by single‐crystal X‐ray crystallography. In [1], each of three [Au(D‐pen‐S)2]3−metalloligands coordinates to two CoIII ions in a bis‐tridentate‐N,O,S mode to form a cyclic AuI3CoIII3 hexanuclear structure, in which three [Co(D‐pen‐N,O,S)2]− octahedral units and six bridging S atoms adopt trans(O) geometrical and R chiral configurations, respectively. In [2]3−, each of three [Au(D‐pen‐S)2]3− metalloligands coordinates to two CoIII ions in a bis‐bidentate‐N,S mode to form a AuI3CoIII2 pentanuclear structure, in which two [Co(D‐pen‐N,S)3]3− units and six bridging S atoms adopt ∧ and R chiral configurations, respectively.

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)

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 reaction of [Ni(aet)2] (aet = −SCH2CH2NH2) with AuI in water gave a S-bridged NiII2AuI2 tetranuclear structure in [Au2{Ni(aet)}2]2+, while the corresponding reaction using [Ni(L)] (L = [−SCH2CH2N=C(CH3)–]2) led to the formation of a NiII4AuI4 octanuclear structure in [Au4{Ni(L)}4]4+. Their molecular structures exhibiting aurophilic interactions were established by X-ray crystallography.

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