Multicomponent halide templating: The effect of structure-directing agents on the assembly of molecular and extended coordination compounds

Healy, Colm; Schmitt, Wolfgang

doi:10.1016/j.ccr.2018.05.014

Cited by 8 publications

(5 citation statements)

References 196 publications

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“…Although halide-templated vanadates exist, , they do not constitute good models for surface-halogenated VO 2 . A majority of these systems possess vanadate ions that encapsulate halide ions, stitched together by electrostatic interactions.…”

Section: Introductionmentioning

confidence: 99%

Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO₂

et al. 2019

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We report the synthesis and characterization of a monochloride-functionalized polyoxovanadate-alkoxide (POV-alkoxide) cluster, which can serve as a molecular model for halogen-doped vanadium oxide (VO2) materials that have recently attracted great interest as advanced materials for energy-saving smart window applications. Chloride-substituted variants of the Lindqvist vanadium-oxide cluster were obtained via two distinct chemical pathways: (1) direct halogenation of the isovalent parent POV-alkoxide architecture, [V6O7(OC2H5)12]−2 with AlCl3 and (2) coordination of a chloride ion to a coordinatively unsaturated vanadium center within a cluster that bears a single oxygen-atom vacancy, [V6O6(OC2H5)12]0. Notably, our direct halogenation constitutes the first example of selective, single-site halide doping of homometallic metal oxide clusters. The chloride-containing compound, [V6O6Cl(OC2H5)12]−1, was characterized by 1H NMR spectroscopy and X-ray crystallography. The electronic structure of the chloride-functionalized POV-alkoxide cluster was established by infrared, electronic absorption, and X-ray photoelectron spectroscopy and revealed formation of a site-differentiated VIII ion upon halogenation. Cyclic voltammetry was employed to assess the electrochemical response of halide doping. A comparison of the Cl-VO2 model to the fully oxygenated cluster, [V6O7(OC2H5)12]−2, provides molecular-level insights into a new proposed mechanism by which halogenation increases the carrier density in solid VO2, namely, through prompting charge separation within the material.

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Section: Introductionmentioning

confidence: 99%

Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO₂

et al. 2019

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“…1) are emerging as unique crystalline materials, and thus have attracted significant interest owing to their fascinating structures and great potential in numerous applications. 1–23 Among the many types of metal-containing clusters, the highly symmetric structures are considered exceptional due to their complexity and beauty, which is inspired by the structure of the ‘star’ molecule, i.e. , buckminsterfullerene (C 60 ) discovered in 1985.…”

Section: Introductionmentioning

confidence: 99%

Platonic and Archimedean solids in discrete metal-containing clusters

Luo

Dong

et al. 2023

Chem. Soc. Rev.

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“…halide-templated assemblies of first row transition metal ions. 41 Far less is known about anionic structure-directing control over oxo clusters in situ, i.e. during their assembly processes in solution.…”

Section: Introductionmentioning

confidence: 99%

“…The considerable templating and recognition properties of inorganic counteranions emerged from supramolecular chemistry research − and attracts increasing attention in bio-, environmental, and inorganic chemistry. ,− However, the full structure-directing potential of counteranions is still far from explored. The majority of synthetic studies are focused on solid state anion template effects on the crystal structure of (oxo) cluster materials, e.g., halide-templated assemblies of first row transition metal ions . Far less is known about anionic structure-directing control over oxo clusters in situ, i.e., during their assembly processes in solution.…”

Section: Introductionmentioning

confidence: 99%

“…The majority of synthetic studies are focused on solid state anion template effects on the crystal structure of (oxo) cluster materials, 40 e.g., halide-templated assemblies of first row transition metal ions. 41 Far less is known about anionic structure-directing control over oxo clusters in situ, i.e., during their assembly processes in solution.…”

Section: ■ Introductionmentioning

confidence: 99%

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Mechanistically Driven Control over Cubane Oxo Cluster Catalysts

et al. 2019

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Predictive and mechanistically driven access to polynuclear oxo clusters and related materials remains a grand challenge of inorganic chemistry. We here introduce a novel strategy for synthetic control over highly sought-after transition metal M4O4 cubanes. They attract interest as molecular water oxidation catalysts that combine features of both heterogeneous oxide catalysts and nature's cuboidal CaMn4O5 center of photosystem II. For the first time, we demonstrate the outstanding structure-directing effect of straightforward inorganic counteranions in solution on the self-assembly of oxo clusters. We introduce a selective counteranion toolbox for the controlled assembly of di(2-pyridyl) ketone (dpk) with M(OAc)2 (M = Co, Ni) precursors into different cubane types. Perchlorate anions provide selective access to type 2 cubanes with the characteristic H2O-M2(OR)2-OH2 edge-site, such as [Co4(dpy-COHO)4(OAc)2(H2O)2](ClO4)2. Type 1 cubanes with separated polar faces [Co4(dpy-COHO)4(L2)4]n+ (L2 = OAc, Cl, or OAc and H2O) can be tuned with a wide range of other counteranions. The combination of these counteranion sets with Ni(OAc)2 as precursor selectively produces type 2 Co/Ni-mixed or Ni4O4 cubanes. Systematic mechanistic experiments in combination with computational studies provide strong evidence for type 2 cubane formation through reaction of the key dimeric building block [M2(dpy-COHO)2(H2O)4]2+ with monomers, such as [Co(dpy-COHO)(OAc)(H2O)3]. Furthermore, both experiments and DFT calculations support an energetically favorable type 1 cubane formation pathway via direct head-to-head combination of two [Co2(dpy-COHO)2(OAc)2(H2O)2] dimers. Finally, the visiblelight-driven water oxidation activity of type 1 and 2 cubanes with tuned ligand environments was assessed. We pave the way to efficient design concepts in coordination chemistry through ionic control over cluster assembly pathways. Our comprehensive strategy demonstrates how retrosynthetic analyses can be implemented with readily available assembly directing counteranions to provide rapid access to tuned molecular materials.

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Multicomponent halide templating: The effect of structure-directing agents on the assembly of molecular and extended coordination compounds

Cited by 8 publications

References 196 publications

Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO₂

Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO₂

Platonic and Archimedean solids in discrete metal-containing clusters

Mechanistically Driven Control over Cubane Oxo Cluster Catalysts

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Multicomponent halide templating: The effect of structure-directing agents on the assembly of molecular and extended coordination compounds

Cited by 8 publications

References 196 publications

Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO2

Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO2

Platonic and Archimedean solids in discrete metal-containing clusters

Mechanistically Driven Control over Cubane Oxo Cluster Catalysts

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Product

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Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO₂

Site-Selective Halogenation of Polyoxovanadate Clusters: Atomically Precise Models for Electronic Effects of Anion Doping in VO₂