A series of liquid crystalline pyridinium and sulfonium derivatives of the [closo-1-CB9H10]- and [closo-1-CB11H12]- anions containing the CH2CH2 linking group was prepared and their molecular and crystal structures were determined by single crystal XRD methods. Thermal and dielectric properties of the series were evaluated in a weakly polar nematic host. The highest extrapolated dielectric anisotropy, Δε, was observed for pyridinium zwitterions (up to 56.
View Article and Find Full Text PDFWe have examined the insertion of carbenes carrying leaving groups into the [-BH] dianion to form the [-1-CBH] anion. The best procedure uses CFSiMe and LiCl as the source of CF. It is simple, convenient and scalable and proceeds with 70-90% yield.
View Article and Find Full Text PDFTwo series of 1,12-bis-zwitterionic derivatives of the [closo-B H ] anion (B), containing either two 4-alkoxypyridinium groups (1B[n]-p) or one 4-alkoxypyridinium and one 4-pentylthianium groups (2B[n]-p), were prepared and their structural (XRD, DFT), thermal, and photophysical properties were compared with those of the analogous derivatives of the [closo-B H ] anion (1A[n]-p and 2A[n]-p). Some 1,7-derivatives of B were isolated and investigated. Both series 1[n] and 2[n] exhibit nematic and crystalline polymorphism; the 12-vertex derivatives (B) have higher transition temperatures than those of the 10-vertex analogues (A).
View Article and Find Full Text PDFAntipodal substitution of the [closo-1-CB11H12](-) anion with a 4-pentylquinuclidinium fragment and alkyl groups in positions C(1) and B(12) gave polar zwitterions 1[n] and 2[n]. The molecular structure of 1[5] was established using X-ray diffraction (XRD) methods: P1̅, a = 15.162(2) Å, b = 16.
View Article and Find Full Text PDFDiazotization of [closo-1-CB11H10-1-R-12-NH2](-)[NMe4](+) (4[NMe4]) in neat 4-methoxypyridine leads to 12-(4-methoxypyridinium) zwitterions [closo-1-CB11H10-1-R-12-(4-MeOC5H4N)] (2) in ∼50% yield. Demethylation of 2 with LiCl in dimethylformamide provides access to 12-pyridones 5[NMe4], which can be O-alkylated with alkyl triflates giving 12-(4-alkoxypyridinium) zwitterions, such as 1. This three-step process is more efficient than direct diazotization of amine 4[NMe4] in neat higher 4-alkoxypyridine.
View Article and Find Full Text PDFThe apparent ionization constants pK(a)' for series of carboxylic acids [closo-1-CB(9)H(8)-1-COOH-10-X](-) (1) and [closo-1-CB(11)H(10)-1-COOH-12-X](-) (2), where X = H, I, n-C(6)H(13), (+)NMe(3), (+)N(2), (+)SMe(2), OC(5)H(11), were measured in EtOH/H(2)O (1/1, v/v) at 24 °C. Correlation analysis of the pK(a)' values using Hammett substituent constants σ(p)(X) gave the reaction constant ρ = 0.87 ± 0.
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