Kolari Kalle, Bulatov Evgeny, Tatikonda Rajendhraprasad, Bertula Kia, Kalenius Elina, Haukka Matti
Department of Chemistry, University of Jyväskylä, P. O. Box 35, FI-40014 Jyväskylä, Finland.
Soft Matter. 2020 Mar 21;16(11):2795-2802. doi: 10.1039/c9sm02186h. Epub 2020 Feb 27.
Square planar platinum(ii) complexes are attractive building blocks for multifunctional soft materials due to their unique optoelectronic properties. However, for soft materials derived from synthetically simple discrete metal complexes, achieving a combination of optical properties, thermoresponsiveness and excellent mechanical properties is a major challenge. Here, we report the rapid self-recovery of luminescent metallogels derived from platinum(ii) complexes of perfluoroalkyl and alkyl derivatives of terpyridine ligands. Using single crystal X-ray diffraction studies, we show that the presence of synergistic platinum-platinum (PtPt) metallopolymerization and fluorine-fluorine (FF) interactions are the major driving forces in achieving hierarchical superstructures. The resulting bright red gels showed the presence of highly entangled three-dimensional networks and helical nanofibres with both (P and M) handedness. The gels recover up to 87% of their original storage modulus even after several cycles under oscillatory step-strain rheological measurements showing rapid self-healing. The luminescence properties, along with thermo- and mechanoresponsive gelation, provide the potential to utilize synthetically simple discrete complexes in advanced optical materials.
由于其独特的光电特性，平面正方形铂（II）配合物是多功能软材料颇具吸引力的构建基元。然而，对于源自合成简单的离散金属配合物的软材料而言，实现光学性质、热响应性和优异机械性能的组合是一项重大挑战。在此，我们报道了由吡啶联配体的全氟烷基和烷基衍生物的铂（II）配合物衍生而来的发光金属凝胶的快速自我恢复。通过单晶X射线衍射研究，我们表明协同的铂-铂（PtPt）金属聚合作用和氟-氟（FF）相互作用的存在是实现分级超结构的主要驱动力。所得的亮红色凝胶显示出存在高度缠结的三维网络和具有（P和M）两种手性的螺旋纳米纤维。即使在振荡阶跃应变流变测量的几个循环后，这些凝胶仍能恢复其原始储能模量的87%，显示出快速的自我修复能力。发光特性以及热响应和机械响应凝胶化作用，为在先进光学材料中利用合成简单的离散配合物提供了潜力。
