Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
ACS Nano. 2012 Nov 27;6(11):9359-65. doi: 10.1021/nn302937t. Epub 2012 Nov 2.
Structure formation, phase behavior, and dynamics of mono-bromo hexa-peri-hexabenzocoronene (HBC-Br) are strongly affected by the confinement of cylindrical nanopores with rigid walls. Using self-ordered nanoporous anodic aluminum oxide (AAO)-containing arrays of aligned nanopores with narrow size distribution as a confining matrix, pronounced alignment of the HBC-Br columns along the nanopore axes was found to be independent of the pore diameter. Hence, arrays of one-dimensional supramolecular HBC-Br wires with the columns uniformly oriented along the wire axes on a macroscopic scale were obtained, unlike with discotics bearing smaller cores. The formation of the crystalline herringbone structure is shifted to lower temperatures in nanopores with diameters of a few hundred nanometers, whereas the formation of this low-temperature phase is completely suppressed when the pore diameter is below 20 lattice parameters. Moreover, the cylindrical confinement affects the disk axial dynamics as well as the distribution of relaxation times.
单体溴代六并苯(HBC-Br)的结构形成、相行为和动力学受到刚性壁圆柱纳米孔的限制强烈影响。使用自组装的含排列整齐的纳米孔的纳米多孔阳极氧化铝(AAO)作为限制矩阵,发现 HBC-Br 柱沿纳米孔轴的明显对齐与孔径无关。因此,与具有较小核心的盘状分子不同,在宏观尺度上获得了一维超分子 HBC-Br 线的阵列,其中柱沿线轴均匀取向。在直径为几百纳米的纳米孔中,晶体人字形结构的形成被转移到更低的温度,而当孔径低于 20 个晶格参数时,这种低温相的形成完全被抑制。此外,圆柱限制还会影响盘的轴向动力学以及弛豫时间分布。