Thermal and Photophysical Properties of Highly Quadrupolar Liquid-Crystalline Derivatives of the [closo-B12 H12 ]2- Anion

Abstract

Two series of 1,12-bis-zwitterionic derivatives of the [closo-B₁₂ H₁₂ ]^2- 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-B₁₀ H₁₀ ]^2- 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). All compounds fluoresce with quantum yields higher for 1B (Φ_F =0.37 for 1B[7]-p and Φ_F =0.27 for 2B[7]-p) than those for the 10-vertex analogues (Φ_F =0.04 for 2A[5]-p). DFT calculations demonstrate an order of magnitude lower first hyperpolarizability, β_(-ω,ω,0) , for 2B[7]-p than that for the 10-vertex analogue 2A[7]-p (1.7×10^-30 vs. 18.9×10^-30 esu at ω=0).

Keywords: boron; cluster compounds; density functional calculations; synthetic design; zwitterions.