Controlling the Reactivity of the [P8W48O184]40− Inorganic Ring and Its Assembly into POMZite Inorganic Frameworks with Silver Ions

Zhan, Cai‐Hong; Zheng, Qi; Long, De‐Liang; Vilà‐Nadal, Laia; Cronin, Leroy

doi:10.1002/ange.201911170

Cited by 10 publications

(1 citation statement)

References 42 publications

(17 reference statements)

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“…This approach provides interesting reaction products shifted from the thermodynamic to the kinetic domain compared to conventional solvent reaction media, allowing the isolation of complex metastable and transient phases instead of stable phases directed by equilibrium conditions (Gopalakrishnan, 1995;Stein et al, 1993;Feng & Xu, 2001). In this context, the family of polyoxometalates (POMs) represents a versatile inorganic constituent because they combine structural diversity and composition with a wide range of useful applications (Pope, 1994(Pope, , 2007Zhan et al, 2019;Du et al, 2014). A particular example of the POM family comes from striking features of Mo VI chemistry in solution.…”

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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Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks

et al. 2020

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The Preyssler polyoxoanion, [NaP5W30O110]14− ({P5W30}), is used as a platform for evaluating the role of nonbridging cations in the formation of transition‐metal‐bridged polyoxometalate (POM) coordination frameworks. Specifically, the assembly architecture of Co2+‐bridged frameworks is shown to be dependent on the identity and amount of alkali or alkaline‐earth cations present during crystallization. The inclusion of Li+, Na+, K+, Mg2+, or Ca2+ in the framework synthesis is used to selectively synthesize five different Co2+‐bridged {P5W30} structures. The influence of the competition between K+ and Co2+ for binding to {P5W30} in dictating framework assembly is evaluated. The role of ion pairing on framework assembly structure and available void volume is discussed. Overall, these results provide insight into factors governing the ability to achieve controlled assembly of POM‐based coordination networks.

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Modification of Multi‐Component Building Blocks for Assembling Giant Chiral Lanthanide‐Titanium Molecular Rings

et al. 2021

Angewandte Chemie

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Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi-component building block [Ln 3 Ti-(HSA) 6 (SA) 4 (H 2 O)] À ({Ln 3 Ti-SA}, H 2 SA = salicylic acid, Ln = Eu/Gd) to form new building blocks {Ln 3 Ti x -MSA} (H 2 MSA = 5-methoxysalicylic acid, x = 1, 2, 3) by constructing [Ti(MSA) 3 ] 2À units. The obtained {Ln 3 Ti x -MSA} can further assemble into a chiral Ln 22 Ti 14 ring with the formulae [Eu 22 Ti 14 (MSA) 48 (HMSA) 22 (CH 3 COO) 4 (H 2 O) 10 (iPrOH)] and [Gd 22 Ti 14 (MSA) 46 (HMSA) 26 (CH 3 COO) 4 (H 2 O) 8 ]. Parallel experiments without Ti 4 + result in linear Ln chains. Detailed analysis shows that the [Ti(MSA) 4 ] 4À unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA) 3 ] 2À further triggers interesting chiralsorting behavior. Finally, the electronic adsorption and magneto-optic responses of these molecular rings are investigated.

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Controlling the Reactivity of the [P₈W₄₈O₁₈₄]⁴⁰⁻ Inorganic Ring and Its Assembly into POMZite Inorganic Frameworks with Silver Ions

Cited by 10 publications

References 42 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

Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks

Modification of Multi‐Component Building Blocks for Assembling Giant Chiral Lanthanide‐Titanium Molecular Rings

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Controlling the Reactivity of the [P8W48O184]40− Inorganic Ring and Its Assembly into POMZite Inorganic Frameworks with Silver Ions

Cited by 10 publications

References 42 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

Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks

Modification of Multi‐Component Building Blocks for Assembling Giant Chiral Lanthanide‐Titanium Molecular Rings

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Product

Resources

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Controlling the Reactivity of the [P₈W₄₈O₁₈₄]⁴⁰⁻ Inorganic Ring and Its Assembly into POMZite Inorganic Frameworks with Silver Ions

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