Charge density matching in templated molybdates

Casalongue, Hernan Sanchez; Choyke, Sarah; Sarjeant, Amy Narducci; Schrier, Joshua; Norquist, Alexander J.

doi:10.1016/j.jssc.2009.02.032

Cited by 21 publications

(29 citation statements)

References 58 publications

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“…The charge densities of the [V 2 Te 2 O 10 ] n 2nÀ layers in 1 and 2 are close to one another, with ranges of À0.01072 to À0.01086 and À0.01032 to À0.1104 e Å À2 , respectively. These differences are small with respect to other systems in which the organic amine acidities show wider variations, 19,20 suggesting that charge density matching does not dictate the difference between [V 2 Te 2 O 10 ] n 2nÀ layer topologies in compounds 1 and 2. While charge density matching is useful for understanding the macroscopic properties of metal oxide anions, specific connectivities and topologies can be more directly influenced by other tertiary interactions.…”

Section: Electron Localization Functions (Elf) Elfs Were Computedmentioning

confidence: 75%

“…32 (2) were calculated using the DMS program, 34 defined by Richards 24 as the molecular surface, and a geometric decomposition method that we reported earlier. 19,20 Lone pair positions were defined as local maxima in the ELF isosurfaces, with radii of 1.5 Å, based upon Galy's work. 35,36 Calculated surface areas are listed in Table 2 Iterative Hirshfeld Charges.…”

Section: Electron Localization Functions (Elf) Elfs Were Computedmentioning

confidence: 99%

“…Charge density matching was quantified using Iterative Hirshfeld partial atomic charges, 22,23 electron localization functions (ELFs), and both molecular24,25 and geometric decomposition19,20 surface areas. These systems were designed to minimize differences associated with composition…”

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confidence: 99%

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Beyond Charge Density Matching: The Role of C–H···O Interactions in the Formation of Templated Vanadium Tellurites

Smith

Blau

Chang

et al. 2011

Crystal Growth & Design

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b S Supporting Information ' INTRODUCTIONTemplated metal oxides have attracted sustained interest for many years, owing to their remarkably high degrees of compositional and structural diversity 1 and for technologically desirable physical properties. 2 However, increasing demand for new materials with enhanced properties has highlighted the lack of design and predictability in the syntheses of such compounds. The greatest limitation lies in our poor understanding of the mechanisms by which these compounds form. 3 While mechanisms have been postulated, 4À8 true design remains elusive. Significant progress has been made in the identification of reaction parameters that most strongly influence the formation of these materials.The primary influence over the structure of the inorganic component is reagent composition. Differences in reactant concentrations are known to directly affect the identity and availability of the primary building units from which the inorganic components are constructed. 9À14 Reactant concentrations are clearly affected by a range of experimental parameters, ranging from the dependence of metal speciation on both pH and temperature to differences associated with source materials and reaction times. The manner in which the inorganic reactants oligomerize and polymerize in the systems described above is thought to be controlled by charge density matching 4,5 between the organic cations and the anionic inorganic synthons. This secondary influence allows for crystallization only after the charge densities of the cationic and anionic components match. The importance of charge density matching has been demonstrated in a range of systems, including silicates, 15À17 oxovanadium phosphates, 18 gallium phosphates, 4,5 molybdates, 19 and vanadium tellurites. 20 Despite the utility of the charge density matching approach, differences in reactant concentrations and amine pK a alone do not wholly dictate the connectivities and structures of the resulting inorganic architectures. Charge density matching cannot differentiate between markedly different inorganic structures that have nearly identical charge densities. For example, we have reported the formation of both [Mo 3 O 10 ] n 2nÀ and [Mo 8 O 26 ] n 4nÀ chains from reactions in which the respective amines had similar pK a 's and were used in nearly identical concentrations. 19 We have also observed both [V 2 Te 2 O 10 ] n 2nÀ chains and [V 2 TeO 8 ] n 2nÀ layers in reactions containing either 1,4-diaminobutane or 1,3-diaminopropane, respectively. 20 In each system, the differences in charge densities of the inorganic components are small. As such, a series of tertiary influences has been proposed, including amine symmetry and hydrogen-bonding preferences. 19À21 This report contains an elucidation and observation of tertiary influences in the formation of new organically templated vanadium tellurites. The NaVO 3 /Na 2 TeO 3 /2,5-dimethylpiperazine and NaVO 3 /Na 2 TeO 3 /2-methylpiperazine systems were explored using composition space analysis, result...

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Section: Electron Localization Functions (Elf) Elfs Were Computedmentioning

confidence: 75%

Section: Electron Localization Functions (Elf) Elfs Were Computedmentioning

confidence: 99%

See 1 more Smart Citation

Beyond Charge Density Matching: The Role of C–H···O Interactions in the Formation of Templated Vanadium Tellurites

Smith

Blau

Chang

et al. 2011

Crystal Growth & Design

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“…Inspection of the decision tree shown in Figure 7 that the primary ammonium cations reside, donating three hydrogen bonds to neighboring oxide anions. In each case, the hydrogen-bond acceptors include the only terminal Se = O oxide anion sites, which exhibit the highest nucleophilicities, [55][56][57][58][59][60][61] as determined using bond valence sums, [35,36] rendering them attractive to hydrogen bond donors. The hydrogen-bonding interactions in these pockets were identified and visualized using non-covalent interaction (NCI) index calculations.…”

Section: Resultsmentioning

confidence: 99%

Probing structural adaptability in templated vanadium selenites

Adler

Olshansky

et al. 2016

Polyhedron

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The structural adaptability of [V 3 O 5 (SeO 3 ) 3 ] n 2nlayers in organically templated vanadium selenites was determined using a three step approach involving (i) 84 reaction study with 14 distinct organic amines and 6 different reaction conditions, (ii) decision tree construction using both dependent and independent variables, and (iii) the derivation of chemical hypotheses.Formation of [V 3 O 5 (SeO 3 ) 3 ] n 2nlayers requires that three criteria be met. First, compound stabilization through hydrogen-bonding with specific nucleophilic oxide ions is needed, requiring the presence of a primary ammonium site on the respective organic amine. Second, layer formation is facilitated through the use of compact ammonium cations that are able to achieve charge density matching with the anionic layers. Third, competition between organic ammonium cations and NH 4 + , which affects product formation, can be controlled through reagent choice and initial reactant concentrations. This approach to elucidate structural adaptability is generalizable and can be applied to a range of chemical systems.

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“…[24] Relevant crystallographic data are listed in [32]) the molecular surface, and a geometric decomposition method that we reported earlier. [33,34] Lone pair positions were defined as local maxima in the ELF isosurfaces, with radii of 1.5 Å, based upon Galy's work. [35,36] Calculated surface areas are listed in Table 2.…”

Section: Synthesismentioning

confidence: 99%