17805-19-5Relevant articles and documents
Geometry and steric effects on the electronic states of aryl-o-carboranes
Kim, So-Yoen,Cho, Yang-Jin,Son, Ho-Jin,Kim, Chul Hoon,Kang, Sang Ook
, p. 152 - 158 (2018)
o-Carborane was used to alter the electronic states of π-conjugated organic aryls, and demonstrated as an effective electron control unit, to tune HOMO and LUMO energies for the electron transfer. Two different types of bis-aryl compounds were selected: one with di-phenyls and its fused fluorenyl, and another with two isomers of naphthyls, α- and β-forms. Among the series of aryl compounds, the second type of naphthyls were more susceptible to electronic alteration and α-isomer of naphthyl showed the most perturbed electronic state. The ground state structures confirmed by crystallographic measurements provide a close correlation of structure and electronic property between photo-responsive aryl groups and o-carborane. In addition to the distance effect, within similar proximity of the aryl functional groups, namely naphthyl case, the steric factor controlled the altered electronic state. HOMO and LUMO energies were estimated and confirmed by cyclic voltammograms and DFT calculations, respectively, and established the authenticity of the electronic alteration. Excited states were calculated by the TD-DFT correlations with the corresponding absorption spectra to illustrate the electronic perturbation in a systematic fashion suggesting that excited states were lowered in regard to the electronic perturbation. Therefore, within bis-aryls-o-carborane series, the following decreasing energy order is observed; α-Np, β-Np, Flu, diPh, and Ph. The final verification of the lowered energy was made according to the electron transfer efficiency between the well-studied iridium based photosensitizer, Ir(ppy)3 and two typical bis-aryls-o-carboranes, α-Np and Ph. The electron transfer efficiency of α-Np is 10 times greater than that of Ph (1.231 × 107 M?1s?1 for α-Np and 9.275 × 105 M?1s?1 for Ph).
Diamine monomer containing carborane structure, dianhydride monomer containing carborane structure and preparation method and application of diamine monomer and dianhydride monomer containing carborane structure
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Paragraph 0058; 0143; 0145, (2021/07/21)
The invention discloses a diamine monomer containing a carborane structure, a dianhydride monomer containing a carborane structure and a preparation method and application of the diamine monomer and the dianhydride monomer. The invention also discloses high-temperature-resistant polyimide containing the carborane structure. The polyimide is prepared by condensation polymerization of the diamine monomer containing the carborane structure and a dianhydride monomer containing the carborane structure. The preparation method comprises the following steps: taking decaborane and alkyne as initial raw materials, preparing a carborane structural unit through addition reaction of the decaborane and the alkyne, and then preparing the diamine monomer containing the carborane structure through nitration reaction and reduction reaction, or preparing the dianhydride monomer containing the carborane structure through oxidation and dehydrating reaction of methyl. The method for preparing the diamine monomer or dianhydride monomer containing the carborane structure has the advantages of simple operation, wide universality, convenient and easily available raw materials, high yield and the like, and is convenient for large-scale production.
Photoarylation of Iodocarboranes with Unactivated (Hetero)Arenes: Facile Synthesis of 1,2-[(Hetero)Aryl]n-o-Carboranes (n=1,2) and o-Carborane-Fused Cyclics
Ni, Hangcheng,Qiu, Zaozao,Xie, Zuowei
supporting information, p. 712 - 716 (2017/01/14)
Photoarylation of iodocarboranes with unactivated arenes/heteroarenes at room temperature has been achieved, for the first time, thus leading to the facile synthesis of a large variety of cage carbon mono(hetero)arylated and di(hetero)arylated o-carboranes. This work represents a clean, efficient, transition-metal-free, and cheap synthesis of functionalized carboranes, which has significant advantages over the known methods.
