Influence of Ester versus Amide Linkers on the Supramolecular Polymerization Mechanisms of Planar BODIPY Dyes

2016 ◽  
Vol 22 (44) ◽  
pp. 15772-15777 ◽  
Author(s):  
Alexander Rödle ◽  
Benedikt Ritschel ◽  
Christian Mück-Lichtenfeld ◽  
Vladimir Stepanenko ◽  
Gustavo Fernández
Author(s):  
Shota Matoba ◽  
Chisako Kanzaki ◽  
Kae Yamashita ◽  
Takahiro Kusukawa ◽  
Gaku Fukuhara ◽  
...  

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yingtong Zong ◽  
Si-Min Xu ◽  
Wenying Shi ◽  
Chao Lu

AbstractThe living supramolecular polymerization technique provides an exciting research avenue. However, in comparison with the thermodynamic spontaneous nucleation, using simple monomers to realize living supramolecular polymerization is hardly possible from an energy principle. This is because the activation barrier of kinetically trapped simple monomer (nucleation step) is insufficiently high to control the kinetics of subsequent elongation. Here, with the benefit of the confinement from the layered double hydroxide (LDH) nanomaterial, various simple monomers, (such as benzene, naphthalene and pyrene derivatives) successfully form living supramolecular polymer (LSP) with length control and narrow dispersity. The degree of polymerization can reach ~6000. Kinetics studies reveal LDH overcomes a huge energy barrier to inhibit undesired spontaneous nucleation of monomers and disassembly of metastable states. The universality of this strategy will usher exploration into other multifunctional molecules and promote the development of functional LSP.


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 ◽  
Author(s):  
Kuikun Yang ◽  
Zhiqing Yang ◽  
Ludan Yue ◽  
Guocan Yu ◽  
Xiangjun Zhang ◽  
...  

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.


2018 ◽  
Vol 57 (52) ◽  
pp. 17189-17193 ◽  
Author(s):  
Qingyun Wan ◽  
Xin-Shan Xiao ◽  
Wai-Pong To ◽  
Wei Lu ◽  
Yong Chen ◽  
...  

2011 ◽  
Vol 123 (50) ◽  
pp. 12162-12167 ◽  
Author(s):  
Calogero Capici ◽  
Yoram Cohen ◽  
Alessandro D'Urso ◽  
Giuseppe Gattuso ◽  
Anna Notti ◽  
...  

2018 ◽  
Vol 130 (52) ◽  
pp. 17435-17439 ◽  
Author(s):  
Qingyun Wan ◽  
Xin-Shan Xiao ◽  
Wai-Pong To ◽  
Wei Lu ◽  
Yong Chen ◽  
...  

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.


Sign in / Sign up

Export Citation Format

Share Document