Nobuto Yoshinari

Thiol-containing amino acids have been known to act as chelating ligands with three potential coordination sites: thiol, amine, and carboxyl groups. Since early reports on the iron-catalyzed oxidation of cysteine in 1884 and the copper-chelating therapy of d-penicillamine in 1956, more than 200 coordination compounds with thiol-containing amino acids have been developed and structurally characterized. The co-presence of hard (amine and carboxylate) and soft (thiolate) Lewis bases in the ligands

In this report, we describe our recent work on the development of a new family of chiral heteroleptic digold(I) metalloligands with mixed diphosphine and d-penicillaminate (d-pen), [Au2 (dppx)(d-pen-S)2 ](2-) (dppx = PPh2 (CH2 )n PPh2 , n = 1-5) and their application for the construction of chiral multinuclear and metallosupramolecular structures. The reactions of the metalloligands with 3d metal ions produce a variety of chiral heterobimetallic structures retaining the digold(I) metalloligand s

The design and creation of ionic crystals that show high mobility of ionic species in the solid state has long been a research topic of considerable attention not only due to the practical applications of these materials but also due to the correlation of such ionic species with ion-transport biological systems. In this work, we report the mobility of alkali metal ions (M = Li⁺, Na⁺, K⁺) in the ionic crystals M₆[Rh₄Zn₄O (l-cystein

Abstract In this account, we focus on the stereochemical and chiral behavior of S-bridged multinuclear and metallosupramolecular coordination compounds that are derived from mononuclear metal complexes with cysteine (H2cys) or penicillamine (H2pen). The mononuclear complexes act as versatile metalloligands with amine and/or carboxyl groups, in addition to the thiol groups, as donor sites, allowing them to form a large variety of coordination compounds in combination with additional metal ions. S

Abstract A unique gold(I)–copper(II) 1D polymeric system, [Cu{Au2(LCn)(pen)2}] (LCn = Ph2P(CH2)nPPh2 (n = 3, 4, and 5); H2pen: penicillamine), which involves three types of helices (single-stranded homochiral helix, single-stranded meso helix, and triple-stranded homochiral helix), is reported. This system was created from linear digold(I) metalloligands, which possess a bis(diphenylphosphino)alkane linker LCn and two-terminal pen coordination arms [Au2(LCn)(pen)2]2−. In this system, the parity

To coil or not to coil: Chiral S-bridged 14-nuclear clusters with 12 free carboxylate groups, [M6M′8(D-pen)12Cl]5− (M=PdII, NiII; M′=CuI, AgI; D-pen=D-penicillaminate; see scheme), prepared from [M(D-pen)2]2− and M′Cl, were organized into heterotrimetallic supramolecular structures in combination with La3+. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as subm

The selective detection of methanol by photoluminescence under environmental conditions has been a great challenge for materials science. Herein, a reversible, turn-on-type photoluminescence triggered by methanol vapor in square-planar palladium(II) and platinum(II) complexes, newly prepared from [MCl2(1,3-bis(diphenylphosphino)propane)] and l-cysteine, is reported. Both the “turn-on” and “turn-off” states of the complexes were crystallographically characterized, which revealed the presence of i

Organic polycarboxylates that exhibit high designability and stability are fundamental building units for constructing coordination and hydrogen-bonded frameworks in supramolecular chemistry. Recently, discrete metal complexes with noncoordinating carboxy moieties (Metal-Organic Carboxylates or Metal-Organic Carboxylic acids; MOCs) have attracted increasing attention as alternatives to organic carboxylates because of their simple synthetic procedures and structural diversity, as well as the ease

The first example of a 1 : 1 metal–organic intercluster compound with +6 charged cations and −6 charged anions was synthesized from [Zn4O{Rh(aet)3}4]6+ (aet = 2-aminoethanethiolate) and [Zn4O{Rh(L-cys)3}4]6− (L-cys = L-cysteinate). Its structure was determined by single-crystal X-ray crystallography, which revealed the formation of a diamondoid (dia) hydrogen-bonding network of the cluster anions, accommodating the cluster cations in its cavities.

pH-dependent architecture: Cluster-based metallosupramolecular compounds, which are composed of [CuI6CuII8(D-pen)12Cl]5− (D-H2pen=D-penicillamine) cluster anions linked by Co2+ and/or K+ cations through D-pen carboxylate groups, were spontaneously synthesized by simple treatment of K[CoIII(D-pen)2] with CuICl in potassium acetate buffer solutions, accompanied by the redox between CoIII and CuI mediated by thiolate. Detailed facts of importance to specialist readers are published as ”Supporting I

Abstract The 1:1 reaction of [PdCl4]2− with d-penicillamine (d-H2pen) gave a S-bridged tetranuclear complex, [Pd4Cl4(d-Hpen)4] ([1]). Complex [1] was converted to a S-bridged trinuclear complex, [Pd3(d-pen)3] ([2]), which was further converted to a mononuclear complex, K2[Pd(d-pen)2] (K2[3]). The reverse conversion of [2] to [1] was also achieved.

A series of chiral M(6)M'(8) cluster compounds having twelve free carboxylate groups, [M(6)M'(8)(D-pen-N,S)(12)X](5-) (M/M'/X = Pd(II)/Ag(I)/Cl(-) ([1](5-)), Pd(II)/Ag(I)/Br(-) ([2](5-)), Pd(II)/Ag(I)/I(-) ([3](5-)), Ni(II)/Ag(I)/Cl(-) ([4](5-)), Pt(II)/Ag(I)/Cl(-) ([5](5-)), Pd(II)/Cu(I)/Cl(-) ([6](5-)); D-H(2)pen = D-penicillamine), in which six cis-[M(D-pen-N,S)(2)](2-) square-planar units are bound to a [M'(8)X](7+) cubic core through sulfur-bridges, was synthesized by the reactions of cis-[

Treatment of fac-[Rh(aet) 3] (aet = 2-aminoethanethiolate) with 2,2'-bis(bromomethyl)-1,1'-biphenyl gave a mononuclear rhodium(III) complex with a nine-membered S, S-chelate ring, fac-[Rh(aet)(L)] (2+) ([ 1] (2+), L = 2,2'-bis(2-aminoethylthiomethyl)-1,1'-biphenyl). Complex [ 1] (2+) afforded a pair of atrop diastereomers, Delta SS( S ax)/Lambda RR( R ax)-[ 1] (2+) ([ 1a] (2+)) and Delta SS( R ax)/Lambda RR( S ax)-[ 1] (2+) ([ 1b] (2+)), which involves the axial chirality ( R ax/ S ax) about a b

Postsynthetic installation of lanthanide cubanes into a metallosupramolecular framework via a single-crystal-to-single-crystal (SCSC) transformation is presented. Soaking single crystals of K₆ [Rh₄ Zn₄ O(l-cys)₁₂ ] (K₆ [1]; l-H₂ cys=l-cysteine) in a water/ethanol solution containing Ln(OAc)₃ (Ln³⁺ =lanthanide ion) results in the exchange of K⁺ by Ln³⁺ with retention of the single crystal

The 1:1 mixing of a pair of enantiomers of a cyclic Au(I)4Co(III)2 hexanuclear complex having penicillaminate (pen) and 1,2-bis(diphenylphosphino)ethane (dppe), [Au4Co2(dppe)2(d-pen)4](2+) (d4-[1](2+)) and [Au4Co2(dppe)2(l-pen)4](2+) (l4-[1](2+)), in solution produced an additional stereoisomer, [Au4Co2(dppe)2(d-pen)2(l-pen)2](2+) (d2l2-[1](2+)), because of the scrambling of [Co(d-pen)2](-) and [Co(l-pen)2](-) units between d4-[1](2+) and l4-[1](2+). Upon crystallization with NO3(-), the three s