<i>o</i>‐Carborane‐based Biphenyl and <i>p</i>‐Terphenyl Derivatives

Morisaki, Yasuhiro; Tominaga, Masato; Ochiai, Takuya; Chujo, Yoshiki

doi:10.1002/asia.201400067

Cited by 38 publications

(18 citation statements)

References 32 publications

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“…1 ), in which the C–C double bonds are localized with the NICS(0) (NICS: nucleus-independent chemical shift) values of –0.7 to –3.4 ppm for exo -C 6 H 4 six-membered ring in benzocarborane derivatives. 6 In contrast, a considerable σ–π conjugation is reported for CB 11 cage-fused heterocyclic anion [1,2-N 3 R-1-CB 11 Cl 10 ] – ( B in Fig. 1 ), leading to an aromatic exo -CBN 3 five-membered ring with a NICS(0) value of –7.8 ppm.…”

Section: Introductionmentioning

confidence: 94%

Synthesis, structure and aromaticity of carborane-fused carbo- and heterocycles

Chan

Xie

2018

Chem. Sci.

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The results of molecular structures, NMR data, and NICS (nucleus-independent chemical shift) and ISE (isomerization stabilization energy) values as well as molecular orbital analyses clearly suggest the presence of considerable aromatic character in the exo five-membered ring of carborane-fused carbo- and heterocycles and considerable conjugation between a 3-D carborane and a fused 2-D π-ring system.

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Section: Introductionmentioning

confidence: 94%

Synthesis, structure and aromaticity of carborane-fused carbo- and heterocycles

Chan

Xie

2018

Chem. Sci.

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“…To construct luminescent solid‐state materials that possess highly sensitive luminochromism, we turned our attention to solid‐state luminescent “element blocks”, which are defined as minimum functional units that are composed of heteroatoms, as a platform for extending conjugated systems . In particular, we focused on globular substituents called o ‐carboranes, which are known as “plastic crystals” .…”

Section: Introductionmentioning

confidence: 99%

Solid‐State Thermochromic Luminescence through Twisted Intramolecular Charge Transfer and Excimer Formation of a Carborane−Pyrene Dyad with an Ethynyl Spacer

et al. 2017

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The pyrene-tetheredc arborane CBEP,w hichexhibited rapid and dramatic luminochromism, was synthesized. Based on opticalm easurements, we found that CBEP exhibited orange emission at room temperature, which was caused by intramolecular charget ransfer in the solid state, and green excimer emissiona t7 7K.W ep roposed that exci-mer formation could be encouraged by introducing as mall amount of steric hindrance with an ethynyl spacer group. We found that o-carborane could suppress aggregationcausedq uenching without the inhibition of excimer formation because of this steric hindrance.[a] Dr.

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“…distances in III, 6 1.739(7) and 1.643(3) Å respectively, are both shorter than those in I, 1.746(4) and 1.651(6) Å respectively. Although the differences are small and not statistically significant, the average C cage -B and C cage -C cage Scheme 3 Interconversion of compounds 2 and 3, and transformation of 3 into 4-6 (4, L = PMe 3 ; 5, L = P(OMe) 3 ; 6; L = t-BuNC).…”

Section: Dalton Transactions Papermentioning

confidence: 75%

“…7% based on B 10 H 14 ), 6 we have first developed an improved synthesis. Although the debronation of III with wet fluoride has been reported and the nido product isolated as the [NMe 4 ] + salt 8 no metal derivatives are currently known.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Further studies of the Enhanced Structural Carborane Effect: tricarbonylruthenium and related derivatives of benzocarborane, dihydrobenzocarborane and biphenylcarborane

2016

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Detailed comparison of the molecular structures of [1,2-μ-(C4H4)-3,3,3-(CO)3-3,1,2-closo-RuC2B9H9] (1) and [1,2-μ-(C4H6)-3,3,3-(CO)3-3,1,2-closo-RuC2B9H9] (2) reveals evidence for an Enhanced Structural Carborane Effect in 1 arising from the involvement of the cage pπ orbitals in the exopolyhedral ring to some degree. A minor co-product in the synthesis of 2 is [η-{1,2-μ-(C4H6)}-3,3-(CO)2-3,1,2-closo-RuC2B9H9] (3). Compounds 2 and 3 are readily interconverted, since heating 2 to reflux in THF or reaction with Me3NO affords 3 which readily reacts with CO to regenerate 2. The η-ene bonding in 3 is also displaced by PMe3, P(OMe)3 and t-BuNC to yield [1,2-μ-(C4H6)-3,3-(CO)2-3-PMe3-3,1,2-closo-RuC2B9H9] (4), [1,2-μ-(C4H6)-3,3-(CO)2-3-P(OMe)3-3,1,2-closo-RuC2B9H9] (5) and [1,2-μ-(C4H6)-3,3-(CO)2-3-t-BuNC-3,1,2-closo-RuC2B9H9] (6), respectively. Structural studies of 4-6, focussing on the Exopolyhedral Ligand Orientation of the {Ru(CO)2L} fragment relative to the C2B3 carborane face, are discussed in terms of the structural trans effects of PMe3, P(OMe)3 and t-BuNC relative to that of CO. An improved synthesis of [1,2-μ-(C6H4)2-1,2-closo-C2B10H10], "biphenylcarborane", is reported following which the first transition-metal derivatives of this species, [1,2-μ-(C6H4)2-3-Cp-3,1,2-closo-CoC2B9H9] (7) and [1,2-μ-(C6H4)2-3,3,3-(CO)3-3,1,2-closo-RuC2B9H9] (8), are prepared. Comparisons of the structures of 7 and 8 with the corresponding benzocarborane derivatives [1,2-μ-(C4H4)-3-Cp-3,1,2-closo-CoC2B9H9] and 1, respectively, suggest that Clar's rule for aromaticity can be applied to polycyclic aromatic hydrocarbons fused onto carborane cages.

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o‐Carborane‐based Biphenyl and p‐Terphenyl Derivatives

Cited by 38 publications

References 32 publications

Synthesis, structure and aromaticity of carborane-fused carbo- and heterocycles

Synthesis, structure and aromaticity of carborane-fused carbo- and heterocycles

Solid‐State Thermochromic Luminescence through Twisted Intramolecular Charge Transfer and Excimer Formation of a Carborane−Pyrene Dyad with an Ethynyl Spacer

Further studies of the Enhanced Structural Carborane Effect: tricarbonylruthenium and related derivatives of benzocarborane, dihydrobenzocarborane and biphenylcarborane

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