Tant Julien, Geerts Yves Henri, Lehmann Matthias, De Cupere Vinciane, Zucchi Gaël, Laursen Bo Wegge, Bjørnholm Thomas, Lemaur Vincent, Marcq Valérie, Burquel Anick, Hennebicq Emmanuelle, Gardebien Fabrice, Viville Pascal, Beljonne David, Lazzaroni Roberto, Cornil Jérôme
Laboratoire de Chimie des Polymères, Université Libre de Bruxelles, CP 206/1 Boulevard du Triomphe, B-1050 Brussels, Belgium.
J Phys Chem B. 2005 Nov 3;109(43):20315-23. doi: 10.1021/jp054778o.
A joint theoretical and experimental study of the electronic and structural properties of liquid crystalline metal-free phthalocyanines bearing a strong potential for charge and exciton transport has been performed. The synthesis of such compounds has been triggered by quantum chemical calculations showing that: (i) hole transport is favored in metal-free phthalocyanines by their extremely low reorganization energy (0.045 eV) and large electronic splittings; and (ii) the efficiency of energy transfer along the one-dimensional discotic stacks is weakly affected by rotational disorder due to the two-dimensional character of the molecules. We have synthesized two metal-free phthalocyanines with different branched aliphatic chains on the gram scale to allow for a full characterization of their solid-state properties. The two compounds self-organize in liquid crystalline mesophases, as evidenced by optical microscopy, differential scanning calorimetry, X-ray powder diffraction, and molecular dynamics simulations. They exhibit a columnar rectangular mesophase at room temperature and a columnar hexagonal mesophase at elevated temperature.
对具有电荷和激子传输强大潜力的无金属液晶酞菁的电子和结构性质进行了理论与实验联合研究。此类化合物的合成是由量子化学计算引发的，计算结果表明：（i）无金属酞菁因其极低的重组能（0.045电子伏特）和大的电子分裂而有利于空穴传输；（ii）由于分子的二维特性，沿一维盘状堆叠的能量转移效率受旋转无序的影响较弱。我们已在克级规模上合成了两种带有不同支链脂肪族链的无金属酞菁，以便对其固态性质进行全面表征。通过光学显微镜、差示扫描量热法、X射线粉末衍射和分子动力学模拟证明，这两种化合物在液晶中间相中自组装。它们在室温下呈现柱状矩形中间相，在高温下呈现柱状六方中间相。
