Abstract
Substitution of each phenyl in 1,3,5-triphenyl-6-oxoverdazyl with three alkoxy groups induces an ordered columnar hexagonal phase (Colh(o)) below 130°C in 1b[n], while in the alkylsulfanyl analogues 1a[n] additional periodicity along the columns was found rendering the phase a true three-dimensional columnar hexagonal phase (Colh(3D)) below 60°C. Both series exhibit broad absorption bands in the visible region with maxima at 540 and 610 nm in series 1a[n] and at 486 and 614 nm in series 1b[n]. Unusual reversible thermochromism is observed in series 1b[n], in which the dark green isotropic phase turns red in the discotic phase. Analysis of 1a[8] revealed redox potentials E0/+11/2 = +0.99 V and E0/ −11/2 = –0.45 V vs. saturated calomel electrode (SCE), while the potentials in the alkoxy analogue 1b[8] are shifted cathodically by 0.16 V. Photovoltaic studies of 1a[8] demonstrated hole mobility of μh = 1.52 × 10−3 cm2 V−1 s−1 in the mesophase with an activation energy Ea = 0.06 ± 0.01 eV. Magnetisation studies of 1a[8] revealed nearly ideal paramagnetic behaviour in either the solid or fluid phase above 200 K and weak antiferromagnetic interactions at low temperatures. In contrast, a noticeable drop of about 4% in μeff was observed during the I→Col phase transition in 1b[8], which coincide with the thermochromic effect.
Acknowledgements
We thank Prof. Andrzej Twardowski for funding SQUID measurements and Ms. Ola Kruczkowska for her technical assistance. The electronic version of the article available at http://pubs.rsc.org/en/content/articlelanding/2012/cc/c2cc33051b.