Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
J Am Chem Soc. 2010 Jun 9;132(22):7668-75. doi: 10.1021/ja910886g.
Coordination of Pt(2+) to a family of tunable Schiff base proligands directs the 12-component self-assembly of disk-shaped Pt(4) rings in a head-to-tail fashion. Aggregation of these S(4) symmetric Pt(4) macrocycles into columnar architectures was investigated by dynamic and static light scattering, NMR spectroscopy, powder X-ray diffraction, and transmission electron microscopy. Data from these experiments support the formation of columnar architectures for all of the structures studied except when bulky tris(4-tert-butylphenyl)methyl substituents were present. In this case, aggregation was limited to dimers in CHCl(3) (K(dim) = 3200 +/- 200 L mol(-1) at 25 degrees C) and a thermodynamic analysis revealed that dimerization is an entropy driven process. Columnar architectures of Pt(4) rings with branched 2-hexyldecyl substituents organize into lyotropic mesophases in nonpolar organic solvents. These new self-assembled supramolecules are promising candidates to access nanotubes with multiple linear arrays of Pt(2+) ions.
Pt(2+)与一系列可调节的席夫碱前体配位，以头尾相接的方式引导 12 组分的盘状 Pt(4)环的自组装。通过动态和静态光散射、NMR 光谱学、粉末 X 射线衍射和透射电子显微镜研究了这些 S(4)对称的 Pt(4)大环聚集成柱状结构的情况。这些实验数据支持除了存在大体积的三(4-叔丁基苯基)甲基取代基的情况之外，所有研究结构都形成柱状结构。在这种情况下，聚集仅限于 CHCl(3)中的二聚体（在 25°C 时，K(dim) = 3200 ± 200 L mol(-1)），热力学分析表明二聚化是一个熵驱动的过程。具有支链 2-己基癸基取代基的 Pt(4)环的柱状结构在非极性有机溶剂中组织成溶致性中间相。这些新的自组装超分子是进入具有多个线性 Pt(2+)离子阵列的纳米管的有前途的候选物。
