Structural conversion from bowl- to ball-type polyoxovanadates: Synthesis of a spherical tetradecavanadate through a chloride-incorporated bowl-type dodecavanadate

Kobayashi, Toshikatsu; Kuwajima, Sho; Kurata, Taisei; Hayashi, Yoshihito

doi:10.1016/j.ica.2014.03.035

Cited by 21 publications

(17 citation statements)

References 43 publications

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“…8 The chloride-centered dodecavanadate, [V 12 O 32 (Cl)] 5– ( 2 ), was synthesized from a cyclic octavanadate, [Cu 2 V 8 O 24 ] 4– . 7 The removal of Cu 2+ ions from the cluster liberates the V 8 cyclic ring that is in close proximity to the rim part of the dodecavanadate cage, and spontaneous condensation leads to the formation of 2 . 7 We also developed the structure transformation reaction of a chloride-centered dodecavanadate, which changes from a bowl shape to a ball shape by the addition of acid or base.…”

Section: Introductionmentioning

confidence: 99%

A Bowl-Type Dodecavanadate as a Halide Receptor

et al. 2017

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The dodecavanadate framework, [V 12 O 32 ] 4– , exhibits a unique bowl-type structure with an open molecular oxide cage having a cavity diameter of 4.4 Å, and different synthetic paths were required to construct the bowl-type structure with a different guest. A new dodecavanadate, {( n -C 4 H 9 ) 4 N} 4 [V 12 O 32 (CH 3 NO 2 )] ( 1 ), is synthesized with a nitromethane guest, which is stacked above the entrance of the hemisphere rather than fully occupying the cavity, and it enables a guest-capturing reaction, while retaining the anionic cage structure. Compound 1 is a good precursor for halide-centered dodecavanadates, {(C 2 H 5 ) 4 N} 5 [V 12 O 32 (X)] (X = Cl – ( 2 ), Br – ( 3 ), and I – ( 4 )). The position of the halide inside the cavity correlates with the ionic radius of the guest; the small chloride ion sat at the far bottom, and the large iodide floated at the entrance. The inclusion reaction rates were estimated through 51 V NMR time-course measurements in nitromethane. The reaction rates increase in the order I – < Br – < Cl – .

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Section: Introductionmentioning

confidence: 99%

A Bowl-Type Dodecavanadate as a Halide Receptor

et al. 2017

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“…In the reported spherical polyoxovanadate frameworks, complexes are formed through at emplate reaction and the structures of the host framework depend on the sizes and shapes of the templates. [8][9][10] On the other hand, the systematic incorporation of guests into the bowl-typehosts enabled us to study the guestexchange properties of different types of guests.…”

Section: Preparation Of Molecular Anion Incorporated Dodecavanadatesmentioning

confidence: 99%

“…On the other hand, fully oxidized VO 5based polyoxovanadates often possessafew lacunary sites, and the missing part of the sphere is small enought op revent guest dissociation. [10] The arrangement of lacunary sites can be rearranged to af urther openf ramework. We reported control of the structureso fc hloride-incorporated dodecavanadates, [V 12 O 32 (Cl)] 5À (V12(Cl)), throughastructure transformation reaction between closed-and bowl-types tructures.…”

Section: Introductionmentioning

confidence: 99%

Small‐Molecule Anion Recognition by a Shape‐Responsive Bowl‐Type Dodecavanadate

Kuwajima

Kikukawa

Hayashi

2017

Chemistry An Asian Journal

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A dodecavanadate, [V O ] , is an inorganic bowl-type host with a cavity entrance with a diameter of 4.4 Å in the optimized structure. Linear, bent, and trigonal planar anions are tested as guest anions and the formation of host-guest complexes, [V O (X)] (X=CN , OCN , NO , NO , HCO , and CH CO ), were confirmed by X-ray crystallographic analyses and a V NMR spectroscopy study. The degree of distortion of the bowl from a regular to an oval shape depends on the type of guest anion. In V NMR spectroscopy, all chemical shifts of the host-guest complexes are clearly shifted after guest incorporation. The incorporation reaction rates for OCN , NO , HCO , and CH CO are much larger than those of NO and halides. The incorporated nonspherical molecular anions in the dodecavanadate host are easily dissociated or exchanged for other anions, whereas spherical halides in the host are preserved without dissociation, even in the presence of the tested anions.

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“…Polyoxovanadates often construct cage-type molecules in a reduced form with a mixed valence state (Mü ller et al, 1998). The condensation of V V polyoxovanadates or the oxidation of those reduced polyoxovanadates produces V V polyoxovanadates such as [ (Kikukawa et al, 2015;Kobayashi et al, 2014). Among the series of polyoxovanadates, [V 12 O 32 ] 4À has a unique bowl-type structure that can accommodate various guest anions in the cavity, for example, it encapsulates not only halides but also molecular anions such as CN À , OCN À , NO 2 À , NO 3 À , HCO 2 À and CH 3 CO 2 À (Kuwajima et al, 2017a,b).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structural characterization of tube-type tetradecavanadates

et al. 2018

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By the reaction of ammonium perchlorate with anion‐incorporated bowl‐type dodecavanadates, viz. [V12O32(X)]5− [X = N3− (1), OCN− and NO3−], tube‐type tetradecavanadates, viz. (NH4)7[V14O38(X)] [X = N3− (2), OCN− (3) and NO3− (4)] were synthesized. The crystal structures of penta(tetraethylammonium) azidododecavanadate nitromethane monosolvate, (C8H20N)5[V12O32(N3)]·CH3NO2, 1, heptaammonium azidotetradecavanadate dimethyl sulfoxide hexasolvate, (NH4)7[V14O38(N3)]·6C2H6OS, 2, heptaammonium cyanatotetradecavanadate dimethyl sulfoxide hexasolvate, (NH4)7[V14O38(OCN)]·6C2H6OS, 3, and heptaammonium nitratotetradecavanadate dimethyl sulfoxide hexasolvate, (NH4)7[V14O38(NO3)]·6C2H6OS, 4, were determined. The tube consists of two layers of V7 rings with a guest anion at the centre. The distances between the incorporated anions and the nearest V atoms are 3.058 (3), 3.039 (6) and 2.811 (9) Å for 2, 3 and 4, respectively, showing that the incorporated anions are stabilized via noncovalent interactions. Two ammonium cations cap both ends of the tube to stabilize the structures via hydrogen‐bonding interactions. Linear OCN− and N3− anions sit on the twofold rotation axes of the tube frameworks and the triangular plane of the NO3− anion deviates from the equatorial plane of the tube by ca 30°.

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Structural conversion from bowl- to ball-type polyoxovanadates: Synthesis of a spherical tetradecavanadate through a chloride-incorporated bowl-type dodecavanadate

Cited by 21 publications

References 43 publications

A Bowl-Type Dodecavanadate as a Halide Receptor

A Bowl-Type Dodecavanadate as a Halide Receptor

Small‐Molecule Anion Recognition by a Shape‐Responsive Bowl‐Type Dodecavanadate

Synthesis and structural characterization of tube-type tetradecavanadates

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