Aggregation of chiral hexanuclear complex-cations into cationic metallosupramolecules with concomitant aggregation of inorganic counter-anions into anionic clusters

Dielectric Jump and Negative Electrostriction in Metallosupramolecular Ionic Crystals

“…The synthesis of [Au I 4 Co III 2 (dppe) 2 ( d -pen) 4 ] 2+ and the growth of its single crystals with monovalent or divalent counteranions were performed according to the method reported in refs 2,3 . The diffraction data for [ 1 ]Cl 2 ∙ n H 2 O was recorded at 100 K with a RIGAKU/MSC Mercury CCD X-ray diffractometer with synchrotron radiation (λ = 0.6889 Å) at PF-AR (NW2A beamline) of the High Energy Accelerator Research Organization (KEK).…”

“…We found that the introduction of hydrophobic dppe (1,2-bis(diphenylphosphino)ethane) into a gold(I)-cobalt(III) coordination system with hydrophilic d -pen affords a cationic Au I 4 Co III 2 hexanuclear complex, [Au 4 Co 2 (dppe) 2 ( d -pen) 4 ] 2+ ([ 1 ] 2+ ), in which two Co III centres are spanned by two [Au I 2 (dppe)( d -pen) 2 ] 2− linkers 1–3 . On crystallization with appropriate monovalent inorganic anions, such as ClO 4 − , NO 3 − , and Cl − or divalent anions such as SiF 6 2− and SO 4 2− , the 6 Au I 4 Co III 2 cations of [ 1 ] 2+ are self-assembled to form huge cationic supramolecular octahedrons, {[ 1 ] 2+ } 6 , which are closely packed into a face centred cubic (fcc) structure with a lattice parameter of a ≈ 3.8 nm.…”

“…Previously, the crystal structures of [ 1 ]X 2 · n H 2 O [X 2  = Cl 2 , Br 2 , (NO 3 ) 2 , (ClO 4 ) 2 , SO 4 , SiF 6 ] were investigated using a laboratory X-ray source at 200 K 2,3 . However, the positions of the water molecules were not clearly determined owing to the limited data quality and their disordered structure.…”

Heterogeneous catalase-like activity of gold(i)–cobalt(iii) metallosupramolecular ionic crystals

“…10 Herein, we report that metallosupramolecular ionic crystals containing cobalt( iii ) centers, [Au I 4 Co III 2 (dppe) 2 ( d -pen) 4 ]X n ([ 1 ]X n , dppe = 1,2-bis(diphenylphosphino)ethane, d -pen = d -penicillaminate, X n = (Cl – ) 2 , (ClO 4 – ) 2 (NO 3 – ) 2 or SO 4 2– , Fig. 1), which were recently synthesized and structurally characterized, 11 exhibit high catalase-like activity under heterogeneous conditions. This class of ionic crystals, which we refer to as ‘non-coulombic ionic solids (NCIS)’, consists of Au I 4 Co III 2 hexanuclear complex cations, [ 1 ] 2+ , and inorganic anions, X – or X 2– , and adopts an unusual non-alternate arrangement of cationic and anionic species governed by non-coulombic interactions; complex cations [ 1 ] 2+ are self-assembled into octahedron-shaped cationic supramolecules, {[ 1 ] 2+ } 6 , and anions X – or X 2– are aggregated into adamantane- or octahedron-shaped anionic clusters, {X – } 10 or {X 2– } 6 (Fig.…”

Metallosupramolecular Structures Derived from a Series of Diphosphine-bridged Digold(I) Metalloligands with Terminald-Penicillamine

“…This result suggested that the monodentate‐ S coordination of the d ‐pen moiety is a key factor for the coordination versatility of the metalloligand. To expand the range of this chemistry, we recently designed a series of diphosphine‐bridged digold(I) metalloligands, [Au 2 (dppx)( d ‐pen‐ S ) 2 ] 2– ([ 1 ] 2– –[ 5 ] 2– ),16–19 by introducing a digold(I) unit with diphosphine as a linker in place of the Au I atom in [Au( d ‐pen‐ S ) 2 ] 3– (dppx = PPh 2 (CH 2 ) n PPh 2 ; n = 1–5) (Figure ).…”