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

Yamada, Mihoko; Yoshinari, Nobuto; Kuwamura, Naoto; Saitô, Tôru; Okada, Satoshi; Maddala, Sai Prakash; Harano, Koji; Nakamura, Eiichi; Yamagami, Kohei; Yamanaka, Kazushi; Sekiyama, A.; Suenobu, Tomoyoshi; Yamada, Yusuke; Konno, Takumi

doi:10.1039/c6sc04993a

Cited by 22 publications

(12 citation statements)

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“…The estimated 10Dq, which is renormalized in the ionic model, can explain the UV and visible absorption spectrum of [Ni 2 {Au 2 (dppe)(D-pen) 2 } 2 ] [11] combined with the so-called Tanabe-Sugano diagram based on the ionic model [39], as displayed in figures 2(d) and (e). Therefore, the electronic description of [Ni 2 {Au 2 (dppe)(D-pen) 2 } 2 ] is similar to that of Co-based complexes coordinated with D-pen [12,21] for which the explicit hybridization effects are not necessary to describe the 3d electronic states. On the other hand, (pdσ) for [Ni{Rh(apt) 3 } 2 ](NO 3 ) 2 is larger than that for the nickel sulfides and oxides within the cluster models because of the consideration of the final-states effect β.…”

Section: Resultsmentioning

confidence: 99%

“…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]. On the other hand, in case of M=Ni as shown in figure 1(a), the chemical analysis suggests that the electronic state of Ni ions in [Ni 2 {Au 2 (dppe)(D-pen) 2 } 2 ] is in high-spin (HS-) Ni 2+ states [11].…”

Section: Introductionmentioning

confidence: 99%

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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: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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“…With the development of nanotechnology, nanozymes are widely used as substitutes of natural enzymes . The reported enzyme‐like activities include the peroxidase‐like activity, superoxide dismutase‐like activity, catalase‐like activity, and so on. However, there are relatively few reports about glucose oxidase (GOx)‐like activity .…”

Section: Introductionmentioning

confidence: 99%

“Non‐Naked” Gold with Glucose Oxidase‐Like Activity: A Nanozyme for Tandem Catalysis

Zhang

Liang

Han

et al. 2018

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It has been widely reported that “naked” gold nanoparticles (Au NPs) without protectors have glucose oxidase (GOx)‐like activity, and the use of protectors can inhibit the GOx‐like activity. Here, “non‐naked” Au NPs with GOx‐like activity are synthesized by using protein as protector. Although “naked” Au NPs have peroxidase‐like activity and GOx‐like activity, the optimal pH ranges of the both activities are obviously different. Fortunately, as‐synthesized “non‐naked” Au NPs show the dual enzyme‐like activities at the same pH. So, “non‐naked” Au NPs can be described as “tandem nanozyme.” As another bonus, the participation of protein protector can stabilize the GOx‐like activity and make Au NPs modifiable. Even though Au NPs are connected with graphene oxide (GO), the GOx‐like activity is still not changed. Further, Au NPs‐GO nanocomposites are applied on the one‐pot nonenzymatic glucose colorimetric detection. The “non‐naked” gold not only broadens the species of tandem nanozymes, but also facilitates the functionalization of nanozymes, which is promising for immunoassay, biosensor, and medical treatment.

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“…Recently, we have developed a new class of digold(I) metalloligands, [Au I 2 (dppx)(D-pen) 2 ] 2− (dppx = PPh 2 [CH 2 ] n PPh 2 , n = 1-5; D-pen = D-penicillaminate), [20][21][22][23][24][25][26][27][28][29] as part of our continuing study on the rational construction of multinuclear and metallosupramolecular coordination compounds based on the metalloligand approach. [30][31][32] Since this class of digold(I) metalloligands possesses hydrophobic phenyl groups as well as hydrophilic amine and carboxyl groups, it is expected that the resulting metal complexes can form an unusual arrangement of ionic species via hydrogen-bonding and π interactions in the solid state.…”

Section: Introductionmentioning

confidence: 99%

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

Pratikha

Inoue

Arai

et al. 2020

J Chinese Chemical Soc

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The reaction of Na[Co III (D-ebp)] (D-H 4 ebp = N,N 0-ethylenebis[D-penicillamine]) with [(Au I Cl) 2 (dppe)] (dppe = 1,2-bis[diphenylphosphino]ethane) gave a cationic Au I 4 Co III 2 hexanuclear complex, [Co III 2 (L Au4)] 2+ ([1] 2+), where [L Au4 ] 4− is a cyclic tetragold(I) metalloligand with a 32-membered ring, [Au I 4 (dppe) 2 (D-ebp) 2 ] 4−. Complex [1] 2+ crystallized with NO 3 − to produce a charge-separation (CS)-type ionic solid of [1](NO 3) 2. In [1](NO 3) 2 , the complex cations are assembled to form cationic supramolecular hexamers of {[1] 2+ } 6 , which are closely packed in a face-centered cubic (fcc) lattice structure. The nitrate anions of [1](NO 3) 2 were accommodated in hydrophilic and hydrophobic tetrahedral interstices of the fcc structure to form tetrameric and hexameric nitrate clusters of {NO 3 − } 4 and {NO 3 − } 6 , respectively. An analogous CS-type ionic solid formulated as [Ni II Co III (L Au4)](NO 3) ([2](NO 3)) was obtained when a 1:1 mixture of Na[Co III (D-ebp)] and [Ni II (D-H 2 ebp)] was reacted with [(Au I Cl) 2 (dppe)], accompanied by the conversion of the diamagnetic, squareplanar [Ni II (D-H 2 ebp)] to the paramagnetic, octahedral [Ni II (D-ebp)] 2−. While the overall fcc structure in [2](NO 3) was similar to that of [1](NO 3) 2 , none of the nitrate anions were accommodated in any hydrophobic tetrahedral interstice, reflecting the difference in the complex charges between [1] 2+ and [2] + .

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

Abstract: The heterogeneous catalase-like activity of ionic crystals consisting of AuI 4CoIII 2 complex cations is studied along with their surface morphologies and oxidation states.

Cited by 22 publications

References 34 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

“Non‐Naked” Gold with Glucose Oxidase‐Like Activity: A Nanozyme for Tandem Catalysis

A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

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