Alkoxy Derivatives of Dodecaborate: Discrete Nanomolecular Ions with Tunable Pseudometallic Properties

Lee, Mark W.; Farha, Omar K.; Hawthorne, M. Frederick; Hansch, Corwin

doi:10.1002/anie.200605126

Cited by 57 publications

(64 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…For non-halide substituted derivatives there were several recent reports by Hawthorne and coworkers describing isolated, slightly Jahn-Teller distorted hypercloso species [B 12 Me 12 ] •-(g = 2⋅0076) and purple [B 12 (OR) 12 ] •-, R = CH 2 Ph and other alkyl groups. [57][58][59] Back-bonding from the electron rich and lone pair-providing alkoxy groups to the electron deficient B 12 cluster was postulated, based on the structural changes such as shrinking B-O distances on oxidation. 58 The alkoxo derivatives were labelled as discrete nanomolecular ions with tunable pseudometallic properties such as metal-like redox reactions 59 while the stable green ion [B 12 (OH) 12 ] •-was structurally analyzed as the Cs + salt, and characterized by EPR (g = 2⋅0042).…”

Section: [B 12 X 12 ] •-mentioning

confidence: 99%

“…43,44 Several theoretical studies have appeared later for species with X = H 45,46 and the attention was also extended to perhalide compounds (X = Hal, n = 6, 8, 9, 10), [47][48][49][50][51][52][53][54][55][56] to peralkylated species such as [B 12 Me 12 ] •-, 57 and to related OR substituted derivatives (R = CH 2 Ph, H). [58][59][60] The substituted 'hypercloso' compounds, typically generated by one-electron oxidation from dianionic closo precursors, are stabilized with electronegative substituents because neither Hal + nor R + or RO + are good leaving groups such as H + . Our focus here will be on the more symmetrical cases, on the compound series [B 6 Hal 6 ] •-(Hal = Cl, Br, I), on well studied [53][54][55][56] [B 9 Br 9 ] •-and on the systems [B 12 X 12 ] •-.…”

Section: Oligoborane Cluster Radicals [B N X N ] •-mentioning

confidence: 99%

See 1 more Smart Citation

Multidimensional potential of boron-containing molecules in functional materials

Kaim

Hosmane

2010

J Chem Sci

View full text Add to dashboard Cite

Boron-containing molecular systems have received much attention under theoretical aspects and from the side of synthetic organic chemistry. However, their potential for further applications such as optically interesting effects such as Non-Linear Optics (NLO), medical uses for Boron Neutron Capture Therapy (BNCT), or magnetism has been recognised only fairly recently. Molecular systems containing boron offer particular mechanisms to accommodate unpaired electrons which may result in stable radicals as spin-bearing materials. Among such materials are organoboron compounds in which the prototypical electron deficient ( 10 B, 11 B) boron vs. carbon centers can accept and help to delocalise added electrons in a 2-dimensionally conjugated π system. Alternatively, oligoboron clusters B n X n k and the related carboranes or metallacarboranes are capable of adding or losing single electrons to form paramagnetic clusters with 3-dimensionally delocalised spin, according to combined experimental studies and quantum chemical calculations. The unique nuclear properties of 10 B are of therapeutic value if their selective transport via appended carbon nanotubes, boron nanotubes, or magnetic nanoparticles can be effected.

show abstract

Section: [B 12 X 12 ] •-mentioning

confidence: 99%

Section: Oligoborane Cluster Radicals [B N X N ] •-mentioning

confidence: 99%

Multidimensional potential of boron-containing molecules in functional materials

Kaim

Hosmane

2010

J Chem Sci

View full text Add to dashboard Cite

show abstract

“…[62] Für Derivate mit Nicht-Halogen-Substituenten beschrieben Hawthorne und Mitarbeiter isolierte, leicht Jahn-Tellerverzerrte hypercloso-[B 12 Me 12 ]C À -Verbindungen (g = 2.0076) und violette [B 12 (OR) 12 ]C À -Verbindungen (R = CH 2 Ph oder andere Alkylgruppen). [55][56][57] Auf Grundlage von Strukturän-derungen wie den bei der Oxidation kleiner werdenden B-OAbständen wurde eine Rückbindung von elektronenreichen Alkoxygruppen, die Elektronenpaare zur Verfügung stellen, zum elektronenarmen B 12 -Cluster postuliert. [56] Die Alkoxoderivate wurden als diskrete nanomolekulare Ionen mit ein- [57] Während das diamagnetische [B 12 (OH) 12 ] 2À bereits vor längerem beschrieben [58] (14) oder (CH 2 ) 3 ), [64b] einschließlich ihrer strukturellen, [64b] theoretischen [64a] und (spektro)elektrochemischen Charakterisierung, [64] wurde erst vor kürzerer Zeit berichtet.…”

Section: [Bunclassified

“…[55][56][57] Auf Grundlage von Strukturän-derungen wie den bei der Oxidation kleiner werdenden B-OAbständen wurde eine Rückbindung von elektronenreichen Alkoxygruppen, die Elektronenpaare zur Verfügung stellen, zum elektronenarmen B 12 -Cluster postuliert. [56] Die Alkoxoderivate wurden als diskrete nanomolekulare Ionen mit ein- [57] Während das diamagnetische [B 12 (OH) 12 ] 2À bereits vor längerem beschrieben [58] (14) oder (CH 2 ) 3 ), [64b] einschließlich ihrer strukturellen, [64b] theoretischen [64a] und (spektro)elektrochemischen Charakterisierung, [64] wurde erst vor kürzerer Zeit berichtet. Den Rechnungen zufolge vergrößert sich der C-C-Abstand bei der Reduktion der neutralen Verbindung zum Radikalanion 14 signifikant, was darauf schließen lässt, dass keine C-C-Bindungen im Radikal vorhanden sind.…”

Section: [Bunclassified

Boratome als Spinträger in zwei‐ und dreidimensionalen Systemen

et al. 2009

View full text Add to dashboard Cite

Die ungewöhnliche Bindung von Bor in Organoboranen oder Oligoborclustern tritt nicht nur in diamagnetischen Molekülen auf, sondern auch in paramagnetischen Systemen, die gemischtvalente Verbindungen und Oligoboran/Carboran‐Clusterradikale umfassen. Das Bild zeigt das einfach besetzte Molekülorbital des Radikalions [C4B8R4H8].− gemäß DFT‐Rechnungen.magnified imageParamagnetische Verbindungen mit mindestens teilweise borzentriertem Elektronenspin lassen sich herstellen, indem entweder durch planare, π‐konjugierte organische Systeme verbrückte Boratome als idealtypische Elektronenakzeptoren verwendet werden oder indem die dreidimensionale, delokalisierte Bindung in mehrkernigen Boranen, Halogenboranen oder Carboranclustern genutzt wird. Das Konzept der Gemischtvalenz kann so von organischen und Übergangsmetallverbindungen auf Verbindungen der Hauptgruppenelemente übertragen werden. Mithilfe der Dichtefunktionaltheorie lässt sich die sehr variable Spinverteilung nachvollziehen.

show abstract

“…15 Among the polyhedral boranes, the family of isomeric icosahedral dicarbaboranes (closo-C 2 B 10 H 12 ) 15 and their metallo-derivatives 16 have received much attention because of their varied chemistry, 17 redox properties, 18 thermal stability, and their potential for applications in the areas of medicine 19 and materials chemistry. 15 Recently we reported a series of MOFs that are derived from closo-1,12-C 2 B 10 H 12 (para-carborane).…”

Section: ■ Introductionmentioning

confidence: 99%

Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

Kennedy¹,

Krungleviciute²,

Clingerman³

et al. 2013

View full text Add to dashboard Cite

A Cu−carborane-based metal−organic framework (MOF), NU-135, which contains a quasi-spherical para-carborane moiety, has been synthesized and characterized. NU-135 exhibits a pore volume of 1.02 cm 3 /g and a gravimetric BET surface area of ca. 2600 m 2 /g, and thus represents the first highly porous carborane-based MOF. As a consequence of the unique geometry of the carborane unit, NU-135 has a very high volumetric BET surface area of ca. 1900 m 2 /cm 3 . CH 4 , CO 2 , and H 2 adsorption isotherms were measured over a broad range of pressures and temperatures and are in good agreement with computational predictions. The methane storage capacity of NU-135 at 35 bar and 298 K is ca. 187 v STP /v. At 298 K, the pressure required to achieve a methane storage density comparable to that of a compressed natural gas (CNG) tank pressurized to 212 bar, which is a typical storage pressure, is only 65 bar. The methane working capacity (5−65 bar) is 170 v STP /v. The volumetric hydrogen storage capacity at 55 bar and 77 K is 49 g/L. These properties are comparable to those of current record holders in the area of methane and hydrogen storage. This initial example lays the groundwork for carborane-based materials with high surface areas.

show abstract

Alkoxy Derivatives of Dodecaborate: Discrete Nanomolecular Ions with Tunable Pseudometallic Properties

Cited by 57 publications

References 21 publications

Multidimensional potential of boron-containing molecules in functional materials

Multidimensional potential of boron-containing molecules in functional materials

Boratome als Spinträger in zwei‐ und dreidimensionalen Systemen

Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

Contact Info

Product

Resources

About