Rotaxanes have attracted more and more attentions because of their diverse applications as sensors,catalysts, and functional materials. The construction of highly ordered and discrete multirotaxanes with the well-defi...Rotaxanes have attracted more and more attentions because of their diverse applications as sensors,catalysts, and functional materials. The construction of highly ordered and discrete multirotaxanes with the well-defined structure remains a challenge. Herein, a symmetric [5]rotaxane with zinc porphyrin as core and the neutral platinum-acetylide as the linkage was synthesized with high yield. The [5]rotaxane was well characterized with NMR spectroscopy and MALDI-TOF mass spectrometry. Interestingly, it was found that the [5]rotaxane showed the controllable aggregation behaviours in different solution compositions. For example, in non-polar solution, the [5]rotaxane could self-assemble into the largescaled solid nanospheres while the nanofibers were formed in polar solvent. Further investigation revealed that the [5]rotaxane displayed J-type aggregation in solution driven by p-p interaction. Notably,the similar structure without DPP[5]A formed the irregular morphology at the same condition,suggesting that the existence of rotaxanes endowed the complex with a relative rigid structure to facilitate the formation of the ordered aggregates.展开更多
The design and self-assembly of pyrene-modified rhomboidal metallodendrimers R1--R6 via directional metal-ligand bonding approach is described. By employing pyrene-containing 120° di-Pt(II) acceptor and appropr...The design and self-assembly of pyrene-modified rhomboidal metallodendrimers R1--R6 via directional metal-ligand bonding approach is described. By employing pyrene-containing 120° di-Pt(II) acceptor and appropri- ate 60° dendritic dipyridyl donors, a variety of [G-1]--[G-3] pyrene-modified rhomboidal metallodendrimers with well-defined shape and size were prepared under mild conditions in high yields. The supramolecular dendrimers were characterized with multinuclear NMR (1H and 31p) and mass spectrometry (CSI-TOF-MS). lsotopically re- solved mass spectrometry data support the existence of the pyrene-modified dendrimers with rhomboidal cavities, and NMR data were consistent with the formation of all ensembles. The shape and size of all rhomboidal den- drimers were investigated with the PM6 semiempirical molecular orbital method. Their primary photochemical properties were studied as well.展开更多
基金financial support from the National Natural Science Foundation of China (No. 21572066)STCSM (No. 16XD1401000)Program for Changjiang Scholars and Innovative Research Team in University
文摘Rotaxanes have attracted more and more attentions because of their diverse applications as sensors,catalysts, and functional materials. The construction of highly ordered and discrete multirotaxanes with the well-defined structure remains a challenge. Herein, a symmetric [5]rotaxane with zinc porphyrin as core and the neutral platinum-acetylide as the linkage was synthesized with high yield. The [5]rotaxane was well characterized with NMR spectroscopy and MALDI-TOF mass spectrometry. Interestingly, it was found that the [5]rotaxane showed the controllable aggregation behaviours in different solution compositions. For example, in non-polar solution, the [5]rotaxane could self-assemble into the largescaled solid nanospheres while the nanofibers were formed in polar solvent. Further investigation revealed that the [5]rotaxane displayed J-type aggregation in solution driven by p-p interaction. Notably,the similar structure without DPP[5]A formed the irregular morphology at the same condition,suggesting that the existence of rotaxanes endowed the complex with a relative rigid structure to facilitate the formation of the ordered aggregates.
文摘The design and self-assembly of pyrene-modified rhomboidal metallodendrimers R1--R6 via directional metal-ligand bonding approach is described. By employing pyrene-containing 120° di-Pt(II) acceptor and appropri- ate 60° dendritic dipyridyl donors, a variety of [G-1]--[G-3] pyrene-modified rhomboidal metallodendrimers with well-defined shape and size were prepared under mild conditions in high yields. The supramolecular dendrimers were characterized with multinuclear NMR (1H and 31p) and mass spectrometry (CSI-TOF-MS). lsotopically re- solved mass spectrometry data support the existence of the pyrene-modified dendrimers with rhomboidal cavities, and NMR data were consistent with the formation of all ensembles. The shape and size of all rhomboidal den- drimers were investigated with the PM6 semiempirical molecular orbital method. Their primary photochemical properties were studied as well.