Transmetalation of Aqueous Inorganic Clusters: A Useful Route to the Synthesis of Heterometallic Aluminum and Indium Hydroxo—Aquo Clusters

Kamunde-Devonish, Maisha K.; Jackson, Milton N.; Mensinger, Zachary L.; Zakharov, Lev N.; Johnson, Darren W.

doi:10.1021/ic403121r

Cited by 22 publications

(29 citation statements)

References 38 publications

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“…1): a planar group of six-coordinate gallium sites which consists of one gallium atom at the center ("core") connected via μ 3 -OH bridges to a "middle ring" of six gallium atoms. 5,10 Single crystal XRD and, as we will show, ssNMR of the Ga 7 In 6 both show that the indium atoms replace only the outer gallium sites as they are incorporated into the cluster. 1a).…”

Section: Introductionmentioning

confidence: 59%

“…Metal-oxide films can be prepared by a variety of methods, but recently, solution processing routes have become viable due to the scalability of depositing large area films. 1,[5][6][7] The semiconductor industry has seen an increasing use of gallium and indium as key components for III/V semiconductors along with other p-block amorphous metal oxide semiconductors. 1,4,5 Aqueous heterometallic nanoscale tridecameric cluster precusors such as In x (μ 3 -OH) 6 (μ 2 -OH) 18 (H 2 O) 24 ] 15+ (x = 1 to 6) have gained attention in the materials science community because of their ability to form high density metal-oxide films.…”

Section: Introductionmentioning

confidence: 99%

“…1,[5][6][7] The semiconductor industry has seen an increasing use of gallium and indium as key components for III/V semiconductors along with other p-block amorphous metal oxide semiconductors. 1,[5][6][7] With industry moving towards more environmentally and economically friendly procedures, the water-based heterometallic hydroxo-aquo complexes have the potential to become a new route for high quality thin films. 1,6,7 The complexes are capable of being prepared from solution-based methods on the gram scale and deposited onto substrates via solution condensation processes such as spin coating and spray coating.…”

Section: Introductionmentioning

confidence: 99%

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Structural study by solid-state⁷¹Ga NMR of thin film transistor precursors

et al. 2015

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Solid-state (71)Ga NMR was used to investigate the structures of several heterometallic Group 13 hydroxo-aquo clusters, [Ga13-xInx (μ3-OH)6(μ2-OH)18(H2O)24](NO3)15 which are envisioned for thin film transistors. The characterization of these clusters in the solid state provides additional information in understanding the synthesis, structure and speciation of these precursors for high-quality, ultrasmooth thin films. Yet important structural information regarding these clusters - including the exact composition, isomeric structure, and coordination environments - were unknown prior to this precise NMR spectroscopy study. These molecular species, termed "Ga13-xInx", contain three types of six-coordinate metal sites, with bridging OH(-) groups and H2O as capping ligands, and we report results on Ga7In6, Ga8In5, Ga10In3, Ga11In2, Ga12In1, and Ga13. Utilizing two magnetic fields (13.9 T and 21.1 T), the solid-state NMR spectra were interpreted in conjunction with computational modeling (using CASTEP) and simulation of spectral lineshapes (using Dmfit). The metal sites are best represented as distorted octahedra, and they exhibit a range of quadrupolar couplings and asymmetry parameters, which can be addressed using longitudinal strain analysis. Until now, there has been speculation about the sites for transmetallation within the synthetic cluster community. Here, we show that Ga NMR is a powerful technique to monitor the transmetallation of In for Ga in the Ga13-xInx clusters, specifically substituting in the "outer ring" sites, and not the "core" or "middle ring".

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Section: Introductionmentioning

confidence: 59%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural study by solid-state⁷¹Ga NMR of thin film transistor precursors

et al. 2015

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“…[4,[12][13][14]. Since recent advances in their synthesis, several reports have demonstrated their use as a greener and more economic route towards fabricating aluminum oxide based materials, specifically thin film transistors (TFTs) [6,10,[15][16][17]. Thus understanding their formation and persistence in solution under varying conditions is essential for understanding the underlying dehydration reactions which produce such thin films and other solid materials.…”

Section: Introductionmentioning

confidence: 99%

Heat capacities and thermodynamics of formation of flat-Al13 nitrate – [Al13(OH)24(H2O)24](NO3)15·11H2O

Reusser

Schliesser

Elliott

et al. 2015

The Journal of Chemical Thermodynamics

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a b s t r a c tWe report enthalpies of formation from the elements and oxides, D f H = À(26195.31 ± 34.46) kJ Á mol À1 and D f;ox H = À(1402.09 ± 33.36) kJ Á mol À1 , for crystalline [Al 13 (l 3 -OH) 6 (l 2 -OH) 18 (H 2 O) 24 ](NO 3 ) 15 Á 11H 2 O (cr) (flat-Al 13 ) measured using aqueous solution room temperature calorimetry. This material is a nitrate salt of a polynuclear aluminum hydroxide ion with thirteen aluminum metal centers, Al 13 15+ .Unlike the e-Al 13 7+ Keggin ion, it contains solely octahedrally coordinated aluminum in a more flat topology. We also report heat capacities from temperatures of (2 to 300) K on this flat-Al 13 nitrate using a Quantum Design Physical Property Measurement System (PPMS). These measurements were used to calculate the standard molar entropy and subsequently the free energy of formation for this material. We observed that during the heat capacity measurements, the flat-Al 13 sample underwent a second order phase transition near T = 214 K.

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“…[1,2] Clusters are desirable precursors for thin films that can be included in devices and test structures due to their solubility in environmentally benign solvents,e ase of deposition on surfaces,pre-organized structure,and lower temperatures of decomposition. Here we showt hat new clusters of the type M[(m-OH) 2 Co(NH 3 ) 4 ] 3 -(NO 3 ) 6 (M = Al, Ga) can be synthesized using Werners century-old cluster as as ubstitutable framework.…”

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confidence: 99%

Stable Heterometallic Cluster Ions based on Werner's Hexol

et al. 2017

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Large aqueous ions are interesting because they are useful in materials science (for example to generate thin films) but also because they serve as molecular models for the oxideaqueous mineral interface where spectroscopyisdifficult. Here we showt hat new clusters of the type M[(m-OH) 2 Co(NH 3 ) 4 ] 3 -(NO 3 ) 6 (M = Al, Ga) can be synthesized using Werners century-old cluster as as ubstitutable framework. We substituted Group 13 metals into the hexol Co[(m-OH) 2 Co-(NH 3 ) 4 ] 3 6+ ion to make diamagnetic heterometallic ions.T he solid-state structure of the hexol-type derivatives were determined by single-crystal XRD and NMR spectroscopya nd confirmed that the solid-state structure persists in solution after dissolution into either D 2 Oor [D 6 ]DMSO.Other compositions besides these diamagnetic ions can undoubtedly be made using asimilar approach,whichconsiderably expands the number of stable aqueous heteronuclear ions. Nanoscale inorganic clusters have been shown to be useful precursors for solution processing of high-quality thin films. [1,2] Clusters are desirable precursors for thin films that can be included in devices and test structures due to their solubility in environmentally benign solvents,e ase of deposition on surfaces,pre-organized structure,and lower temperatures of decomposition. [3] While various sol-gel based approaches satisfy these conditions,m any use hybrid inorganic-organic mixtures that require large amounts of energy to process and have the potential to leave behind organic/ carbon contaminants.B ecause of this,t here is an eed for precursors with minimal organic components that can be deposited from solution, to realize alow-energy and efficient method for producing thin films for avariety of applications. [4] Thew ell-known, venerable "Werner hexol" cluster (M = Co in Scheme 1) was originally synthesized in 1898 by Jçrgensen, [5] and later studied by Alfred Werner to provide the first evidence for molecular chirality in the absence of carbon. [6,7] Later synthetic work by Kauffman and others developed methods to prepare additional salts and hydrates of this structure type. [7b] This cluster contained only cobalt ions and inorganic ligands such as hydroxide and ammine,and provided awealth of information about coordination chemistry and the structure of inorganic molecules. [7] Importantly, this cluster-through its D and L twisted isomers-provided definitive proof that chirality was not solely the domain of organic molecules.Despite spectacular examples of historically significant inorganic coordination clusters,t he rational design of allinorganic clusters can be challenging,w ith clusters often resulting from serendipity.T his likely results from undesirable reactions (or precipitation) that produce the thermodynamically more stable bulk metal oxide/hydroxide. [8] It is for this reason that many successful strategies use organic ligands to suppress continued polymerization, resulting in elegant ligand-supported aqueous coordination clusters, [9] which are typically undesirable as...

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Transmetalation of Aqueous Inorganic Clusters: A Useful Route to the Synthesis of Heterometallic Aluminum and Indium Hydroxo—Aquo Clusters

Cited by 22 publications

References 38 publications

Structural study by solid-state⁷¹Ga NMR of thin film transistor precursors

Structural study by solid-state⁷¹Ga NMR of thin film transistor precursors

Heat capacities and thermodynamics of formation of flat-Al13 nitrate – [Al13(OH)24(H2O)24](NO3)15·11H2O

Stable Heterometallic Cluster Ions based on Werner's Hexol

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Transmetalation of Aqueous Inorganic Clusters: A Useful Route to the Synthesis of Heterometallic Aluminum and Indium Hydroxo—Aquo Clusters

Cited by 22 publications

References 38 publications

Structural study by solid-state71Ga NMR of thin film transistor precursors

Structural study by solid-state71Ga NMR of thin film transistor precursors

Heat capacities and thermodynamics of formation of flat-Al13 nitrate – [Al13(OH)24(H2O)24](NO3)15·11H2O

Stable Heterometallic Cluster Ions based on Werner's Hexol

Contact Info

Product

Resources

About

Structural study by solid-state⁷¹Ga NMR of thin film transistor precursors

Structural study by solid-state⁷¹Ga NMR of thin film transistor precursors