A redox active triad nanorod constructed from covalently interlinked organo-hexametalates

Bayaguud, Aruuhan; Zhang, Jin; Khan, Rao Naumaan Nasim; Hao, Jian; Wei, Yongge

doi:10.1039/c4cc06297c

Cited by 38 publications

(18 citation statements)

References 30 publications

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“…Despite the simultaneous occurrence of different species in solution, there are limited examples of crystal structures built up by two POM entities. Among these examples, only a few have been reported involving the combination of heteropolyoxomolybdates and isopolyoxomolybdates (Li et al, 2017;Wang et al, 2006;Yu et al, 2011;Mu ¨ller et al, 2000;Zhang et al, 2010) or containing isopolyoxomolybdates and an isopolyoxovanadate (Bayaguud et al, 2014). Fewer examples are reported that include the concomitance of only two isopolyoxomolybdates in a unique crystal structure.…”

Section: Introductionmentioning

confidence: 99%

Concomitance of octamolybdate isomers in metastable crystal structures isolated using homoleptic Co^II/Co^III complexes as structure-directing templates

Atencio¹,

Briceño²,

Bruno-Colmenárez³

et al. 2021

Acta Crystallogr Sect B

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Exploiting the kinetic domain provided by hydrothermal conditions, it was possible to isolate three transient metastable crystal structures, each bearing concomitant pairs of octamolybdate isomers, namely, α–β, γ–β or βcs–βgp stabilized by distinctive homoleptic [Co(bpy)3] n+ (bpy = 2,2′-bipyridine; n = 2 or 3) cations generated in situ: [Co(bpy)3]4[(α-Mo8O26)(β-Mo8O26)]·5H2O (1), [NH4][Co(bpy)3][(γ-Mo8O26)0.5(β-Mo8O26)0.5]·4H2O (2) and [Co(bpy)3]2[(βcs-Mo8O26)0.5(βgp-Mo8O26)]·12H2O (3). Solid 1 with the space group P21/n and unit-cell parameters a = 22.160 (6), b = 14.209 (3), c = 24.641 (4) Å, β = 99.10 (2)° and V = 7661 (3) Å3 resulted in the same crystal structure as that synthesized previously under different conditions by Sun et al. [J. Mol. Struct. (2005), 741, 149–153]. Factors directing the reaction, such as product composition and phase stability, were monitored by analysis of the PXRD patterns of the bulk solids obtained under different experimental conditions. The relative proportions of the mixed phases 1–3 or their stabilization are highly dependent on the initial Co:Mo molar ratio and the reaction temperature. In particular, an increase in temperature induces the transformation of 1–3 into more thermodynamically stable phases formed by one-dimensional coordination polymers [Co(bpy)2(β-Mo8O26)0.5] n (4) and [(MoO3)(bpy)] n (5). The crystal structures of 1–3 correspond to molecular salts self-assembled by C—H...O—Mo, C...H and H...H intermolecular contacts. A Hirshfeld surface analysis for 1 showed that the C...H and H...H interactions represent an average of 51.8% of the total cation–cation intermolecular contacts. In contrast, these interactions are vastly reduced in 2 (23.0%) and 3 (average 28.5% for both isomers). EPR experiments indicated that the crystal structures of 1 and 3 are paramagnetic, and that for 2 is diamagnetic. The paramagnetism of 3 stems from the in situ formation of [Co(bpy)3]3+ in a high-spin configuration. The structure-directing properties of the [Co(bpy)3] n+ cations in the isolation and self-assembly of concomitant octamolybdate isomers are also described from the viewpoint of crystal engineering.

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Section: Introductionmentioning

confidence: 99%

Concomitance of octamolybdate isomers in metastable crystal structures isolated using homoleptic Co^II/Co^III complexes as structure-directing templates

Atencio¹,

Briceño²,

Bruno-Colmenárez³

et al. 2021

Acta Crystallogr Sect B

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“…37,38 Furthermore, nanorod triads, in which POMs bis-functionalised with tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2) were used as the linker between two Mo6, have also been reported and displayed redox activity and photochromism. [39][40][41] However, the formation of POM-POM hybrids using this approach is currently mostly limited to hexamolybdates and requires more complex reaction conditions involving the use of additional reagents, such as N,N'-dicyclohexylcarbodiimide (DCC). 42 On the other hand, the formation of triol-functionalised HPOMs can be achieved for a much wider range of POM structure types via a simpler one-pot synthesis involving just mixing of the starting materials under reflux.…”

Section: Introductionmentioning

confidence: 99%

Versatile Post-functionalisation Strategy for the Formation of Modular Organic-Inorganic Polyoxometalate Hybrids

Marcano

Anyushin

Lentink

et al. 2021

Preprint

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Hybrid structures incorporating different organic and inorganic constituents are emerging as a very promising class of materials since they synergistically combine the complementary and diverse properties of the individual components. Hybrid materials based on polyoxometalates (POMs) are particularly interesting due to the versatile catalytic, redox, electronic, and magnetic properties of this large family of metal-oxo clusters, yet the combination of different clusters has been scarcely reported. Hence, herein we propose a novel and general strategy for combining multiple types of metal-oxo clusters in a single hybrid molecule. Two novel hybrid POM structures (HPOMs) bis-functionalised with dipentaerythritol (R-POM1-R; R = (OCH2)3CCH2OCH2C(CH2OH)) were synthesised as building-blocks for the formation of heterometallic hybrid triads (POM2-R-POM1-R-POM2). Such a modular approach resulted in the formation of four novel heterometallic hybrids combing the Lindqvist {V6}, Anderson-Evans {XMo6} (X = Cr or Al) and trisubstituted Wells-Dawson {P2V3W15} POM structures. Their formation was confirmed by multinuclear Nuclear Magnetic Resonance (NMR), infrared (IR) and UV-Vis spectroscopy, as well as Mass Spectrometry, Diffusion Ordered Spectroscopy (DOSY) and elemental analysis. Their thermal stability was also examined by Thermogravimetric Analysis (TGA), which showed that overall the HPOM triads exhibit higher thermal stability than comparable hybrid structures containing only one type of POM. The one-pot synthesis of these novel compounds was achieved in high yields in aqueous and organic media under simple reflux conditions, without the need of any additives, and could be applied for creating other hybrid materials based on a variety of metal-oxo cluster building-blocks.

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“…The [V 6 O 13 {(OCH 2 ) 3 C-CH 2 OH} 2 ] 2− anion has been used as platform for various post-functionalization [29,30]. The use of -NH 2 as functional group is also convenient for post-functionalization of POMs [17,21,22,31,32], however it is difficult to obtain the [V 6 O 13 {(OCH 2 ) 3 C-NH 2 } 2 ] 2− anion by reacting tris(hydroxymethyl)aminomethane (Tris) with vanadate precursors. Indeed the direct reaction of Tris with decavanadate in dry dimethylacetamide (90 °C overnight) led to the desired compound with a very low yield (< 6%) [21].…”

Section: Introductionmentioning

confidence: 99%

N-tert-butoxycarbonyl (BOC) protected [V₆O₁₃{(OCH₂)₃CNH₂}₂]²⁻: synthesis, structural characterization, and solution behavior

Bamba

Falaise

Gbassi

et al. 2020

Journal of Coordination Chemistry

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Herein, we report the synthesis of N-tert-butoxycarbonyl (BOC) protected [V 6 O 13 {(OCH 2) 3 C-NH 2 } 2 ] 2built from the Lindqvist-type hexavanadate. The reaction of di-tert-butyl dicarbonate (BOC 2 O) with tris(hydroxymethyl)aminomethane (Tris) led to the organic derivative [(OCH 2) 3 C-NH(BOC)] that reacts with the decavanadate in dimethylacetamide (DMA) to form the [V 6 O 13 {(OCH 2) 3 C-NH(BOC)} 2 ] 2anions. The tetrabutylammonium (TBA +) salt of this hybrid polyoxovanadate, TBA 2 [V 6 O 13 {(OCH 2) 3 C-NH(BOC)} 2 ]•2DMA, has been characterized in the solid-state by single crystal X-ray diffraction and infrared spectroscopy, and in solution by multinuclear (1 H, 13 C and 51 V) and DOSY NMR, and UV-visible spectroscopy.

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A redox active triad nanorod constructed from covalently interlinked organo-hexametalates

Abstract: A novel nanorod-like inorganic-organic hybrid compound based on polyoxometalate architectures and organic linkers was successfully synthesized, which exhibits reversible reduction-oxidation properties and fascinating photochromism under sunlight illumination.

Cited by 38 publications

References 30 publications

Concomitance of octamolybdate isomers in metastable crystal structures isolated using homoleptic Co^II/Co^III complexes as structure-directing templates

Concomitance of octamolybdate isomers in metastable crystal structures isolated using homoleptic Co^II/Co^III complexes as structure-directing templates

Versatile Post-functionalisation Strategy for the Formation of Modular Organic-Inorganic Polyoxometalate Hybrids

N-tert-butoxycarbonyl (BOC) protected [V₆O₁₃{(OCH₂)₃CNH₂}₂]²⁻: synthesis, structural characterization, and solution behavior

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A redox active triad nanorod constructed from covalently interlinked organo-hexametalates

Abstract: A novel nanorod-like inorganic-organic hybrid compound based on polyoxometalate architectures and organic linkers was successfully synthesized, which exhibits reversible reduction-oxidation properties and fascinating photochromism under sunlight illumination.

Cited by 38 publications

References 30 publications

Concomitance of octamolybdate isomers in metastable crystal structures isolated using homoleptic CoII/CoIII complexes as structure-directing templates

Concomitance of octamolybdate isomers in metastable crystal structures isolated using homoleptic CoII/CoIII complexes as structure-directing templates

Versatile Post-functionalisation Strategy for the Formation of Modular Organic-Inorganic Polyoxometalate Hybrids

N-tert-butoxycarbonyl (BOC) protected [V6O13{(OCH2)3CNH2}2]2−: synthesis, structural characterization, and solution behavior

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Concomitance of octamolybdate isomers in metastable crystal structures isolated using homoleptic Co^II/Co^III complexes as structure-directing templates

Concomitance of octamolybdate isomers in metastable crystal structures isolated using homoleptic Co^II/Co^III complexes as structure-directing templates

N-tert-butoxycarbonyl (BOC) protected [V₆O₁₃{(OCH₂)₃CNH₂}₂]²⁻: synthesis, structural characterization, and solution behavior