Supramolecular Polymers, Formed by Orthogonal Non‐covalent Interactions*

Supramolecular polymers are linear chains of low molar mass monomers held together by reversible and directional non-covalent interactions, which can form gels or highly viscous solutions if the self-assembled chains are sufficiently long and rigid. The viscosity of these solutions can be controlled by adding monofunctional compounds, which interact with the chain extremities: chain stoppers. We have synthesized new substituted ureas and thioureas and tested them as chain stoppers for a bis-urea based supramolecular polymer. In particular, the bis-thiourea analogue of the bis-urea monomer is shown not to form a supramolecular polymer, but a good chain stopper, because it is a strong hydrogen bond donor and a weak acceptor. Moreover, all substituted ureas tested reduce the viscosity of the supramolecular polymer solutions, but the best chain stopper is obtained when two hydrogen bond acceptors are placed in the same relative position as for the monomer and when no hydrogen bond donor is present.

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Dynamers: Dynamic Molecular and Supramolecular Polymers

Australian Journal of Chemistry ◽

10.1071/ch10035 ◽

2010 ◽

Vol 63 (4) ◽

pp. 611 ◽

Cited By ~ 95

Author(s):

Jean-Marie Lehn

Keyword(s):

Dynamic Properties ◽

The Other ◽

Supramolecular Polymers ◽

Polymer Science ◽

Covalent Bonds ◽

Dynamic Materials ◽

Non Covalent Interactions ◽

Reversible Covalent ◽

Covalent Interactions ◽

Molecular Nature

Dynamers are defined as constitutional dynamic polymers, i.e. polymeric entities whose monomeric components are linked through reversible connections and have therefore the capacity to modify their constitution by exchange and reshuffling of their components. They may be either of supramolecular or molecular nature depending on whether the connections are non-covalent interactions or reversible covalent bonds. They are formed respectively either by polyassociation with interactional recognition or by polycondensation with functional recognition between the connecting subunits. Both types are illustrated by specific examples implementing hydrogen bonding on one hand and formation of imine-type bonds on the other. The dynamic properties confer to dynamers the ability to undergo adaptation and driven evolution under the effect of external chemical or physical triggers. Dynamers thus are constitutional dynamic materials resulting from the application of the principles of constitutional dynamic chemistry to polymer science.

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Controlling Exchange Pathways in Dynamic Supramolecular Polymers by Controlling Defects

10.26434/chemrxiv.13655864.v1 ◽

2021 ◽

Author(s):

Anna Lucia de Marco ◽

Davide Bochicchio ◽

Andrea Gardin ◽

Giovanni Doni ◽

Giovanni M. Pavan

Keyword(s):

Machine Learning ◽

Coarse Grained ◽

Supramolecular Polymers ◽

Enhanced Sampling ◽

Key Factors ◽

Molecular Approaches ◽

Molecular Determinants ◽

Non Covalent Interactions ◽

Covalent Interactions ◽

Intrinsic Dynamic

Supramolecular fibers, composed of monomers that self-assemble directionally via non-covalent interactions, are ubiquitous in nature and of great interest in chemistry. In these structures, the constitutive monomers continuously exchange in-and-out the assembly according to a well-defined supramolecular equilibrium. However, unraveling the exchange pathways and their molecular determinants constitutes a non-trivial challenge. Here we combine coarse-grained modeling, enhanced sampling, and machine learning to investigate the key factors controlling the monomer exchange pathways in synthetic supramolecular polymers having an intrinsic dynamic behavior. We demonstrate how the competition of directional vs. non-directional interactions between the monomers controls the creation/annihilation of defects in the supramolecular polymers, from where monomers exchange proceeds. This competition determines the exchange pathway, dictating whether a fiber statistically swaps monomers from the tips or all along its length. Finally, thanks to their generality, our models allow the investigation of molecular approaches to control the exchange pathways in these dynamic assemblies.

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Supramolecular concepts and approaches in corrosion and biofouling prevention

Corrosion Reviews ◽

10.1515/corrrev-2018-0105 ◽

2019 ◽

Vol 37 (3) ◽

pp. 187-230 ◽

Cited By ~ 10

Author(s):

Viswanathan S. Saji

Keyword(s):

Supramolecular Chemistry ◽

Supramolecular Structures ◽

Surface Coatings ◽

Self Assembled Monolayers ◽

Supramolecular Polymers ◽

Assembled Monolayers ◽

Metal Organic ◽

Non Covalent Interactions ◽

Current Research Interest ◽

Covalent Interactions

AbstractSupramolecular chemistry is one of the exciting branches of chemistry where non-covalent interactions between molecules and the ensuing supramolecular structures have been studied for various applications. The present review provides a comprehensive outlook on the applications and potentials of supramolecular chemistry in corrosion and biofouling prevention. Reported works associating supramolecular chemistry with corrosion are systematically discussed under two sections: (i) surface coatings and (ii) corrosion inhibitors that include supramolecular polymers, host-guest inclusion compounds, organic-inorganic hybrid materials, and supramolecular structures of graphene, crown ethers, self-assembled monolayers, etc. Different strategies for making antifouling surfaces based on block copolymers/gel systems, host-guest systems, and metal-organic structures are briefed. Cyclodextrin and mesoporous silica-based host-guest systems are extensively discussed, as they are the most prominent materials of current research interest. Future potentials for developments are presented. The review is expected to be beneficial to enhance supramolecular chemistry-related research and development in corrosion and biofouling prevention.

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Interplay between non-covalent interactions in 1D supramolecular polymers based on 1,4-bis(iodoethynyl)benzene

Physical Chemistry Chemical Physics ◽

10.1039/d0cp05917j ◽

2021 ◽

Vol 23 (5) ◽

pp. 3531-3542

Author(s):

Lucia González ◽

Sara Graus ◽

Blanca Gaspar ◽

Sheila Espasa ◽

Adrián Velázquez-Campoy ◽

...

Keyword(s):

Isothermal Titration Calorimetry ◽

Supramolecular Interactions ◽

Supramolecular Polymers ◽

Titration Calorimetry ◽

Theoretical Methods ◽

Non Covalent Interactions ◽

Covalent Interactions

Supramolecular interactions of three halogen-bonded co-crystals of 1,4-bis(iodoethynyl)benzene (p-BIB) with organic bromide salts have been studied via isothermal titration calorimetry and theoretical methods including NCI methodology.

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Tuning Energy Landscapes and Metal-Metal Interactions in Supramolecular Polymers regulated by Coordination Geometry

Chemical Science ◽

10.1039/d1sc00416f ◽

2021 ◽

Author(s):

Nils Bäumer ◽

Krishnan Kartha Kalathil ◽

Stefan Buss ◽

Ivan Maisuls ◽

Jasnamol P. Palakkal ◽

...

Keyword(s):

Photophysical Properties ◽

Energy Landscape ◽

Supramolecular Polymers ◽

Coordination Geometry ◽

Energy Landscapes ◽

Metal Interactions ◽

Metal Metal ◽

Non Covalent Interactions ◽

Self Assembled ◽

Covalent Interactions

Herein, we exploit coordination geometry as a new tool to regulate the non-covalent interactions, photophysical properties and energy landscape of supramolecular polymers. To this end, we have designed two self-assembled...

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Controlling Exchange Pathways in Dynamic Supramolecular Polymers by Controlling Defects

10.26434/chemrxiv.13655864 ◽

2021 ◽

Author(s):

Anna Lucia de Marco ◽

Davide Bochicchio ◽

Andrea Gardin ◽

Giovanni Doni ◽

Giovanni M. Pavan

Keyword(s):

Machine Learning ◽

Coarse Grained ◽

Supramolecular Polymers ◽

Enhanced Sampling ◽

Key Factors ◽

Molecular Approaches ◽

Molecular Determinants ◽

Non Covalent Interactions ◽

Covalent Interactions ◽

Intrinsic Dynamic

Supramolecular fibers, composed of monomers that self-assemble directionally via non-covalent interactions, are ubiquitous in nature and of great interest in chemistry. In these structures, the constitutive monomers continuously exchange in-and-out the assembly according to a well-defined supramolecular equilibrium. However, unraveling the exchange pathways and their molecular determinants constitutes a non-trivial challenge. Here we combine coarse-grained modeling, enhanced sampling, and machine learning to investigate the key factors controlling the monomer exchange pathways in synthetic supramolecular polymers having an intrinsic dynamic behavior. We demonstrate how the competition of directional vs. non-directional interactions between the monomers controls the creation/annihilation of defects in the supramolecular polymers, from where monomers exchange proceeds. This competition determines the exchange pathway, dictating whether a fiber statistically swaps monomers from the tips or all along its length. Finally, thanks to their generality, our models allow the investigation of molecular approaches to control the exchange pathways in these dynamic assemblies.

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Strategies to create hierarchical self-assembled structures via cooperative non-covalent interactions

Chemical Society Reviews ◽

10.1039/c4cs00497c ◽

2015 ◽

Vol 44 (8) ◽

pp. 2543-2572 ◽

Cited By ~ 235

Author(s):

Christina Rest ◽

Ramesh Kandanelli ◽

Gustavo Fernández

Keyword(s):

Self Assembly ◽

Supramolecular Polymers ◽

Supramolecular Systems ◽

Multiple Systems ◽

Cooperative Phenomena ◽

Non Covalent Interactions ◽

Self Assembled ◽

High Degree ◽

Covalent Interactions ◽

Degree Of Order

Cooperative phenomena exhibit the basis for the hierarchical self-assembly of multiple systems in nature. Motivated by the high degree of order in these structures, a large number of supramolecular polymers have been designed whose aggregation follows a cooperative pathway. Herein, we have classified the supramolecular systems depending on the cooperative non-covalent forces driving their formation.

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Controlling Exchange Pathways in Dynamic Supramolecular Polymers by Controlling Defects

10.26434/chemrxiv.13655864.v2 ◽

2021 ◽

Author(s):

Anna Lucia de Marco ◽

Davide Bochicchio ◽

Andrea Gardin ◽

Giovanni Doni ◽

Giovanni M. Pavan

Keyword(s):

Machine Learning ◽

Coarse Grained ◽

Supramolecular Polymers ◽

Enhanced Sampling ◽

Key Factors ◽

Molecular Approaches ◽

Molecular Determinants ◽

Non Covalent Interactions ◽

Covalent Interactions ◽

Intrinsic Dynamic

Supramolecular fibers, composed of monomers that self-assemble directionally via non-covalent interactions, are ubiquitous in nature and of great interest in chemistry. In these structures, the constitutive monomers continuously exchange in-and-out the assembly according to a well-defined supramolecular equilibrium. However, unraveling the exchange pathways and their molecular determinants constitutes a non-trivial challenge. Here we combine coarse-grained modeling, enhanced sampling, and machine learning to investigate the key factors controlling the monomer exchange pathways in synthetic supramolecular polymers having an intrinsic dynamic behavior. We demonstrate how the competition of directional vs. non-directional interactions between the monomers controls the creation/annihilation of defects in the supramolecular polymers, from where monomers exchange proceeds. This competition determines the exchange pathway, dictating whether a fiber statistically swaps monomers from the tips or all along its length. Finally, thanks to their generality, our models allow the investigation of molecular approaches to control the exchange pathways in these dynamic assemblies.

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