scholarly journals Non-equilibrium supramolecular polymerization

2017 ◽  
Vol 46 (18) ◽  
pp. 5476-5490 ◽  
Author(s):  
Alessandro Sorrenti ◽  
Jorge Leira-Iglesias ◽  
Albert J. Markvoort ◽  
Tom F. A. de Greef ◽  
Thomas M. Hermans
Keyword(s):  
Supramolecular Chemistry ◽  
Supramolecular Polymers ◽  
Supramolecular Polymerization ◽  
Equilibrium Polymerization ◽  
Non Equilibrium

Supramolecular polymers can reside in four distinct thermodynamic states. The preparation protocol and mechanistic insights allow to identify each one of them. Going beyond equilibrium polymerization is an exciting new direction in the field of supramolecular chemistry.

scholarly journals Supramolecular Systems Containing B–N Frustrated Lewis Pairs of Tris(pentafluorophenyl)borane and Triphenylamine Derivatives

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 ◽  
...  
Keyword(s):  
Materials Science ◽  
Supramolecular Polymers ◽  
Frustrated Lewis Pairs ◽  
Paramagnetic Resonance ◽  
Donor And Acceptor ◽  
Donor Acceptor ◽  
Noncovalent Polymers ◽  
Electron Paramagnetic ◽  
Supramolecular Polymerization ◽  
Lewis Pairs

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.

scholarly journals Living supramolecular polymerization of fluorinated cyclohexanes

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Oleksandr Shyshov ◽  
Shyamkumar Vadakket Haridas ◽  
Luca Pesce ◽  
Haoyuan Qi ◽  
Andrea Gardin ◽  
...  
Keyword(s):  
Dipole Moment ◽  
Self Assembly ◽  
Materials Science ◽  
Helical Structure ◽  
The Self ◽  
Supramolecular Polymers ◽  
Aliphatic Compound ◽  
Double Helical Structure ◽  
Key Driver ◽  
Supramolecular Polymerization

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.

scholarly journals Controlling the length of porphyrin supramolecular polymers via coupled equilibria and dilution-induced supramolecular polymerization

2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Elisabeth Weyandt ◽  
Luigi Leanza ◽  
Riccardo Capelli ◽  
Giovanni M. Pavan ◽  
Ghislaine Vantomme ◽  
...  
Keyword(s):  
Complex Systems ◽  
Self Assembly ◽  
Chiral Discrimination ◽  
Coarse Grained ◽  
Supramolecular Polymers ◽  
Supramolecular System ◽  
Precise Control ◽  
Aggregate Morphology ◽  
The Individual ◽  
Supramolecular Polymerization

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.

Supramolecular polymerization of supramonomers: a way for fabricating supramolecular polymers

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

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

Non‐Equilibrium Polymerization of Cross‐β Amyloid Peptides for Temporal Control of Electronic Properties

2020 ◽  
Vol 59 (32) ◽  
pp. 13506-13510 ◽  
Author(s):  
Subhajit Bal ◽  
Chandranath Ghosh ◽  
Tapan Ghosh ◽  
Ratheesh K. Vijayaraghavan ◽  
Dibyendu Das
Keyword(s):  
Electronic Properties ◽  
Temporal Control ◽  
Amyloid Peptides ◽  
Β Amyloid ◽  
Equilibrium Polymerization ◽  
Non Equilibrium

Cooperative supramolecular polymerization of phosphorescent alkynyl-gold(i)–isocyanide complexes

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

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

Water-induced helical supramolecular polymerization and gel formation of an alkylene-tethered perylene bisimide dyad

2017 ◽  
Vol 53 (1) ◽  
pp. 168-171 ◽  
Author(s):  
Xu Lin ◽  
Hiroki Kurata ◽  
Deepak D. Prabhu ◽  
Mitsuaki Yamauchi ◽  
Tomonori Ohba ◽  
...  
Keyword(s):  
Aqueous Media ◽  
Supramolecular Polymers ◽  
Gel Formation ◽  
Perylene Bisimide ◽  
Supramolecular Polymerization ◽  
Lyotropic Mesophases

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.

scholarly journals Non-Equilibrium Generation of Catalytic Supramolecular Polymers of Pre-RNA Nucleobases

2021 ◽  
Author(s):  
Syed Pavel Afrose ◽  
Chiranjit Mahato ◽  
Pooja Sharma ◽  
Lisa Roy ◽  
Dibyendu Das
Keyword(s):  
Information Storage ◽  
Supramolecular Polymers ◽  
Polymer Backbone ◽  
Available Energy ◽  
Reversible Covalent ◽  
The Stability ◽  
Equilibrium Polymers ◽  
Emergence Of Life ◽  
Hydrolysis Of ◽  
Non Equilibrium

<p>Bioenergetics played critical roles for the chemical emergence of life where available energy resources drove the generation of primitive polymers and fueled early metabolism. Further, apart from information storage, the catalytic roles of primitive nucleic acid fragments have also been argued to be important for biopolymer evolution. Herein, we have demonstrated the non-equilibrium generation of catalytic supramolecular polymers of a possible proto-RNA building block (melamine) driven by a thermodynamically activated ester of low molecular weight. We utilized reversible covalent linkage to install a catalytic imidazole moiety in the polymer backbone. This resulted in energy dissipation via hydrolysis of the substrate predominantly from the assembled state and subsequent disassembly, thus installing kinetic asymmetry in the energy consumption cycle. Non-catalytic analogues led to kinetically stable polymers while inactivated substrates were unable to drive the polymerization. The non-equilibrium polymers of the pre-RNA bases were capable to spatiotemporally bind to a model cofactor. Notably, presence of an exogenous aromatic base augmented the stability of the polymers, reminiscent to what the molecular midwives did during early evolution. </p>

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