State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials, and Department of Chemistry, The University of Hong Kong, Hong Kong SAR, China.
Chem Asian J. 2011 Nov 4;6(11):3011-9. doi: 10.1002/asia.201100316. Epub 2011 Sep 6.
A series of phosphorescent terpyridyl platinum(II) complexes with ancillary biphenylacetylide ligands, namely, [(R(3)tpy)PtC≡C(biphenyl)]X (R=tBu, H, or Et(2)N; tpy=2,2';6',2''-terpyridyl; X is an anion) were synthesized and structurally characterized by various spectroscopic techniques and X-ray diffraction methods. Despite a lack of long alkyl chain(s) or hydrogen-bonding motif(s), complexes [(tpy)PtC≡C(biphenyl)]Cl and [(tBu(3)tpy)PtC≡C(biphenyl)]X (X=Cl, ClO(4), PF(6), or BF(4)) were found to gelate water and organic solvents, respectively. The self-aggregation of these complexes in solutions and the resulting gels were investigated with variable-temperature (VT) (1)H NMR spectroscopy, polarized optical microscopy, and absorption/emission spectroscopy. SEM micrographs on dry gels revealed entangled nanofibers with diameters of 20-40 nm and lengths of tens of micrometers. Powder X-ray diffraction (PXRD) study revealed various degrees of crystallinity of these fibrillar nanostructures. The substituents on both the terpyridyl and acetylide ligands and counterion of these complexes play a profound but concerted role in tuning the intermolecular metal···metal and/or π-π interactions, and hence the gelation properties.
一系列具有辅助联苯乙炔配体的磷光三吡啶铂(II)配合物，即[(R(3)tpy)PtC≡C(biphenyl)]X（R=tBu、H 或 Et(2)N；tpy=2,2';6',2''-三联吡啶；X 是阴离子），通过各种光谱技术和 X 射线衍射方法进行了合成和结构表征。尽管缺乏长烷基链或氢键模体，但配合物[(tpy)PtC≡C(biphenyl)]Cl 和 [(tBu(3)tpy)PtC≡C(biphenyl)]X（X=Cl、ClO(4)、PF(6)或 BF(4))分别被发现能够胶凝水和有机溶剂。这些配合物在溶液中和所得凝胶中的自组装通过变温（VT）（1）H NMR 光谱、偏振光显微镜和吸收/发射光谱进行了研究。干燥凝胶的 SEM 显微照片显示出直径为 20-40nm 且长度为数十微米的纠缠纳米纤维。粉末 X 射线衍射（PXRD）研究表明这些纤维状纳米结构具有不同程度的结晶度。这些配合物的三吡啶和乙炔配体上的取代基以及抗衡离子在调节分子间金属···金属和/或π-π相互作用方面发挥了深远但协同的作用，从而调节了凝胶性能。
