Construction of [2]rotaxane-based supramolecular polymers driven by wheel-stopper π⋯π interactions

2018 ◽  
Vol 54 (82) ◽  
pp. 11634-11637 ◽  
Author(s):  
Xianqiang Zeng ◽  
Hongmei Deng ◽  
Xueshun Jia ◽  
Lei Cui ◽  
Jian Li ◽  
...  

A new strategy for supramolecular polymerization is designed and presented, which is based on the wheel-stopper charge-transfer interactions of [2]rotaxanes.

2015 ◽  
Vol 51 (16) ◽  
pp. 3434-3437 ◽  
Author(s):  
Shilu Wang ◽  
Yiliang Wang ◽  
Zhenxia Chen ◽  
Yuejian Lin ◽  
Linhong Weng ◽  
...  

The marriage of exo-wall interactions and endo-cavity inclusion provides a new strategy for the construction of supramolecular polymers from unfunctionalized neutral receptors.


2021 ◽  
Vol 03 (02) ◽  
pp. 174-183
Author(s):  
P. Chidchob ◽  
S. A. H. Jansen ◽  
S. C. J. Meskers ◽  
E. Weyandt ◽  
N. P. van Leest ◽  
...  

The introduction of a chemical additive to supramolecular polymers holds high potential in the development of new structures and functions. In this regard, various donor- and acceptor-based molecules have been applied in the design of these noncovalent polymers. However, the incorporation of boron–nitrogen frustrated Lewis pairs in such architectures is still rare despite their many intriguing properties in catalysis and materials science. The limited choices of suitable boron derivatives represent one of the main limitations for the advancement in this direction. Here, we examine the use of the commercially available tris(pentafluorophenyl)borane with various triphenylamine derivatives to create supramolecular B–N charge transfer systems. Our results highlight the importance of a proper balance between the donor/acceptor strength and the driving force for supramolecular polymerization to achieve stable, long-range ordered B–N systems. Detailed analyses using electron paramagnetic resonance and optical spectroscopy suggest that tris(pentafluorophenyl)borane displays complex behavior with the amide-based triphenylamine supramolecular polymers and may interact in dimers or larger chiral aggregates, depending on the specific structure of the triphenylamines.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Oleksandr Shyshov ◽  
Shyamkumar Vadakket Haridas ◽  
Luca Pesce ◽  
Haoyuan Qi ◽  
Andrea Gardin ◽  
...  

AbstractThe development of powerful methods for living covalent polymerization has been a key driver of progress in organic materials science. While there have been remarkable reports on living supramolecular polymerization recently, the scope of monomers is still narrow and a simple solution to the problem is elusive. Here we report a minimalistic molecular platform for living supramolecular polymerization that is based on the unique structure of all-cis 1,2,3,4,5,6-hexafluorocyclohexane, the most polar aliphatic compound reported to date. We use this large dipole moment (6.2 Debye) not only to thermodynamically drive the self-assembly of supramolecular polymers, but also to generate kinetically trapped monomeric states. Upon addition of well-defined seeds, we observed that the dormant monomers engage in a kinetically controlled supramolecular polymerization. The obtained nanofibers have an unusual double helical structure and their length can be controlled by the ratio between seeds and monomers. The successful preparation of supramolecular block copolymers demonstrates the versatility of the approach.


2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Elisabeth Weyandt ◽  
Luigi Leanza ◽  
Riccardo Capelli ◽  
Giovanni M. Pavan ◽  
Ghislaine Vantomme ◽  
...  

AbstractMulti-component systems often display convoluted behavior, pathway complexity and coupled equilibria. In recent years, several ways to control complex systems by manipulating the subtle balances of interaction energies between the individual components have been explored and thereby shifting the equilibrium between different aggregate states. Here we show the enantioselective chain-capping and dilution-induced supramolecular polymerization with a Zn2+-porphyrin-based supramolecular system when going from long, highly cooperative supramolecular polymers to short, disordered aggregates by adding a monotopic Mn3+-porphyrin monomer. When mixing the zinc and manganese centered monomers, the Mn3+-porphyrins act as chain-cappers for Zn2+-porphyrin supramolecular polymers, effectively hindering growth of the copolymer and reducing the length. Upon dilution, the interaction between chain-capper and monomers weakens as the equilibria shift and long supramolecular polymers form again. This dynamic modulation of aggregate morphology and length is achieved through enantioselectivity in the aggregation pathways and concentration-sensitive equilibria. All-atom and coarse-grained molecular simulations provide further insights into the mixing of the species and their exchange dynamics. Our combined experimental and theoretical approach allows for precise control of molecular self-assembly and chiral discrimination in complex systems.


2014 ◽  
Vol 5 (20) ◽  
pp. 5895-5899 ◽  
Author(s):  
Qiao Song ◽  
Fei Li ◽  
Xinxin Tan ◽  
Liulin Yang ◽  
Zhiqiang Wang ◽  
...  

This communication describes a new method of fabricating supramolecular polymers through supramolecular polymerization of supramonomers.


2019 ◽  
Vol 11 (19) ◽  
pp. 17894-17901 ◽  
Author(s):  
Zhiqian Xu ◽  
Tingting Zhang ◽  
Yue Gu ◽  
Futong Liu ◽  
He Liu ◽  
...  

2019 ◽  
Vol 10 (23) ◽  
pp. 3210-3216 ◽  
Author(s):  
Cong Wang ◽  
Ze Chen ◽  
Mingyang Liu ◽  
Hua Zhong ◽  
Feng Wang

In this work, coil–rod–coil organogold(i) complexes have been successfully assembled into supramolecular polymers with green phosphorescent emission signal.


2017 ◽  
Vol 53 (1) ◽  
pp. 168-171 ◽  
Author(s):  
Xu Lin ◽  
Hiroki Kurata ◽  
Deepak D. Prabhu ◽  
Mitsuaki Yamauchi ◽  
Tomonori Ohba ◽  
...  

Linking two perylene bisimide dyes through an alkylene tether enforces aggregation in aqueous media, affording helical supramolecular polymers that can form gel-like lyotropic mesophases.


2014 ◽  
Vol 67 (6) ◽  
pp. 887 ◽  
Author(s):  
Ting-Hong Huang ◽  
Min-Hua Zhang

Based on the ligands N,N′-bis(pyridin-2-ylmethylene)benzene-1,4-diamine (pmb) and N,N′-bis(pyridin-2-ylmethylene)biphenyl-4,4′-diamine (pmbb), the three compounds [Cu2(pmb) (PPh3)2(Cl)2] (1), [Cu2(pmbb)(CH3CN)2(PPh3)2](BF4)2·2DMF (2), and [Ag2(pmbb)(PPh3)2] (ClO4)2 (3) have been synthesised and characterised. Structural analysis reveals that all of these complexes contain 1D supramolecular arrays, with different variations in π-stacking patterns and intermolecular C–H···π interactions. Crystal structures of 1 and 2 contain 1D tape-like arrays formed by C–H···π and π···π interactions, and an ordered-layer-lattice of DMF and BF4– in 2 is located between the one-dimensional array. For 3, π-stacking interactions lead to the construction of 1D supramolecular arrays and a 2D network. The results indicate that C–H···π and π···π interactions play an important role in the construction of the supramolecular structure. In addition, the absorption peaks of complexes 1 and 3 in the solid state at room temperature show intraligand charge transfer and metal-to-ligand charge transfer absorptions. The optical and fluorescent properties of 2 were also studied in acetonitrile solution at room temperature.


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