Park Jaehyeon, Lee Ji Ha, Jaworski Justyn, Shinkai Seiji, Jung Jong Hwa
Department of Chemistry & Research Institute of Natural Science, Gyeongsang National University , Jinju 660-701, Republic of Korea.
Inorg Chem. 2014 Jul 21;53(14):7181-7. doi: 10.1021/ic500266f. Epub 2014 Jul 10.
We have synthesized a calix[4]arene derivative (1) containing terpyridine and showed that gelation occurred in the presence of Pt(2+) in DMSO/H2O of varying compositions. Gelation was presumably mediated by the Pt-Pt and π-π stacking interactions. The scanning electron microscopy image of the xerogel showed a spherical structure with diameter of 1.8-2.1 μm. Interestingly, the metallogel showed strong luminescence enhancement, which was dependent on the DMSO/H2O ratio of the solvent. We examined the effects of concentration, temperature, and time resolution on the luminescence emission of both the gel 1-Pt(2+) and the sol 1-Pt(2+). The luminescence lifetimes of the metallogel were particularly long, on the order of several microseconds. The luminescence lifetimes were also strongly dependent on the solvent composition. We also determined the thermodynamic parameters for the self-assembly of the gel by the Birks kinetic scheme. Furthermore, the rheological properties of the metallogels in the presence of more than 4.0 equiv of Pt(2+) were independent of the concentration of Pt(2+) applied.
我们合成了一种含有三联吡啶的杯[4]芳烃衍生物（1），并表明在不同组成的二甲基亚砜/水体系中，在Pt(2+)存在的情况下会发生凝胶化。凝胶化大概是由Pt-Pt和π-π堆积相互作用介导的。干凝胶的扫描电子显微镜图像显示出直径为1.8 - 2.1μm的球形结构。有趣的是，金属凝胶表现出强烈的发光增强，这取决于溶剂的二甲基亚砜/水比例。我们研究了浓度、温度和时间分辨率对凝胶1-Pt(2+)和溶胶1-Pt(2+)发光发射的影响。金属凝胶的发光寿命特别长，约为几微秒。发光寿命也强烈依赖于溶剂组成。我们还通过伯克斯动力学方案确定了凝胶自组装的热力学参数。此外，在存在超过4.0当量的Pt(2+)时，金属凝胶的流变性质与所施加的Pt(2+)浓度无关。
