Metallosupramolecular Structures Derived from a Series of Diphosphine-bridged Digold(I) Metalloligands with Terminal<scp>d</scp>-Penicillamine

Yoshinari, Nobuto; Konno, Takumi

doi:10.1002/tcr.201600026

Cited by 38 publications

(14 citation statements)

References 159 publications

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“…Sulfur-containing transition metal (TM) compounds possess a variety of fascinating properties such as metalinsulator transitions [1,2], thermoelectric effects [3,4], and superconductivity [5]. Among them, many sulfurcoordinating TM multinuclear complexes have been synthesized through stepwise synthesis, which have a potential for new physical properties [6][7][8][9]. For instance, the single-crystalline [M 2 {Au 2 (dppe)(D-pen) 2 } 2 ]X 2 [dppe denotes 1, 2-bis(diphenylphosphino)-ethane, M=Co, Ni, and X 2 stand for anions] of which M sites are unusually stabilized in an octahedral structure bonded by the coordinations with two aliphatic thiolato, two amine, and two carboxylate donors [10,11], shows catalyst-like reactions for M=Co [12].…”

Section: Introductionmentioning

confidence: 99%

The prominent charge-transfer effects of trinuclear complexes with nominally high nickel valences

et al. 2019

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Recently synthesized Rh-Ni trinuclear complexes hexacoordinated with sulfur ions, 3-aminopropanethiolate (apt) metalloligand [Ni{Rh(apt) 3 } 2 ](NO 3 ) n (n=2, 3, 4), are found to be chemically interconvertible between the nominal Ni 2+ and Ni 4+ states. In order to clarify the origins of their interconvertible nature and the stability of such a high oxidation state as the tetravalency from the physical point of view, we have systematically investigated the local 3d electronic structures of [Ni{Rh(apt) 3 } 2 ](NO 3 ) n by means of soft x-ray core-level absorption spectroscopy (XAS). The experimental data have been reproduced by the single-site configuration-interaction cluster-model simulations, which indicate that the charge-transferred configurations are more stable than the nominal d-electron-number configuration for n=3, 4 leading to the prominent charge-transfer effects. These are also supported by S K-edge XAS of [Ni{Rh(apt) 3 } 2 ](NO 3 ) n . Our results imply that the found charge-transfer effects have a key role to realize the interconvertible nature as well as the stability of the high oxidization state of the Ni ions.

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Section: Introductionmentioning

confidence: 99%

The prominent charge-transfer effects of trinuclear complexes with nominally high nickel valences

et al. 2019

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“…It has been recognized that a variety of polynuclear and supramolecular coordination compounds are created from thiol-containing amino acids, such as l -cysteine ( l -H 2 cys), d -penicillamine ( d -H 2 pen), and their derivatives, in combination with 3d and 4d transition metal ions, because these amino acids can adopt various coordination modes to multiple metal centres by using amine, carboxyl, and/or thiol groups dependent on their protonation/deprotonation states 1–4 . 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 .…”

Section: Introductionmentioning

confidence: 99%

“…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.…”

Section: Introductionmentioning

confidence: 99%

Dielectric Jump and Negative Electrostriction in Metallosupramolecular Ionic Crystals

Nakazawa

Yamanaka

Okumura

et al. 2018

Sci Rep

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In natural ionic solids, cationic and anionic species are alternately arranged to minimize electrostatic energy. Aggregation of identical ionic species is commonly prohibited due to the repulsive, long-range nature of Coulombic interactions. Recently, we synthesized unique ionic solids, [AuI4CoIII2(dppe)2(d-pen)4]X2·nH2O (dppe = 1,2-bis(diphenylphosphino)ethane, d-pen = d-penicillaminate), in which complex cations are self-assembled into a cationic supramolecular octahedron, while monovalent or divalent inorganic anions are aggregated into an anomalous anionic cluster accommodating several water molecules. This quite unusual aggregation manner originates from various molecular-level non-Coulombic interactions such as hydrogen bonds and CH-π interactions; thus, this class of ionic solids is referred to as non-Coulombic ionic solids, abbreviated as NCISs. Herein, we report that the NCISs with a peculiar charge-separated (CS) structure in a cubic lattice show a negative, isotropic electrostriction phenomenon that has never been found in any ionic solids, as well as an anomalously large relaxer-like dielectric jump phenomenon reaching to an application level of ε′/ε0 ~ 105. The appearance of these phenomena was explained by the cooperative dynamics of inorganic anions and dipolar water molecules in the pliable anionic clusters that are surrounded by a rather robust cationic metallosupramolecular framework with a meso-scopic scale.

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“…[23,34] This system involves a1 16-nuclear Au I 72 Cd II 40 Na I 4 metallosupramolecular cage-of-cage, [35][36][37][38] which was produced in the course of our ongoing study on the construction of polynuclear and metallosupramolecular structures using [Au 3 (tdme)(d-Hpen) 3 ]( H 3 L Au3 ; tdme = 1,1,1-tris(diphenylphosphinomethyl)ethane, d-H 2 pen = d-penicillamine) as am etalloligand (Scheme 1). [39,40] In the crystal, the cage-of-cage molecules are packed in ah uge cubic lattice with ac ell volume comparable to that of some protein crystals, such that large interstices are formed between the cage-of-cage molecules. Of particularn ote is the very fast, complete exchange of all the Na + and Cd 2 + ions in the cageof-cage by Cu 2 + ions in aS CSC transformation manner,c onstructing an analogousA u I 72 Cu II 44 cage-of-cage just by soaking the crystals in aqueous Cu(NO 3 ) 2 (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

A 116‐Nuclear Metallosupramolecular Cage‐of‐Cage Showing Multistep Single‐Crystal‐to‐Single‐Crystal Transformation

Imanishi

Wahyudianto

Kojima

et al. 2020

Chemistry A European J

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Here au nique single-crystal-to-single-crystal (SCSC) transformationo fa116-nuclear Au I 72 Cd II 40 Na I 4 cageof-cage( 2 CdNa )i sreported, which was created from at rigold(I) metalloligand with d-penicillamine by way of a9 -nuclear Au I 6 Cd II 3 cage (1). Cage-of-cage 2 CdNa is composedo f1 2 cages of 1 that are linked by 4C d 2 + and 4N a + ions, with its surface being covered by 12 NO 3 À ions to form ad iscrete, spherical molecule with ad iameter ca. 4.7 nm. In crystal 2 CdNa ,t he cage-of-cage molecules are packed in ac ubic lattice with ah uge cell volumeo fc a. 4.5 10 5 3 , so as to have large interstices with diameters of more than 3nm. Upon soakingc rystals 2 CdNa in aqueous Cu(NO 3 ) 2 ,a ll Cd 2 + and Na + were quicklye xchanged by Cu 2 + to producea na nalogous Au I 72 Cu II 44 cage-of-cage (2 Cu )i naSCSC manner.P rolonged soakingl ed to the SCSC transformation to anothers upramolecular structure (2' Cu )c onsisting of 152-nuclear Au I 72 Cu II 80 cage-of-cages that are alternately H-bonded with the Au I 72 Cu II 44 cage-of-cages. 2' Cu showed the accommodationo f MoO 4 2À and the conversion of MoO 4 2À to b-Mo 8 O 26 4À in the crystal, with retention of single-crystallinity. Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.org/10.1002/chem.201904275.Scheme1.Synthetic routes to 1 and 2 CdNa .C olor codes: red,A u; cream, Cd; purple, Na.

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

Cited by 38 publications

References 159 publications

The prominent charge-transfer effects of trinuclear complexes with nominally high nickel valences

The prominent charge-transfer effects of trinuclear complexes with nominally high nickel valences

Dielectric Jump and Negative Electrostriction in Metallosupramolecular Ionic Crystals

A 116‐Nuclear Metallosupramolecular Cage‐of‐Cage Showing Multistep Single‐Crystal‐to‐Single‐Crystal Transformation

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