Multiscale Self-Assembly of a Phenyl-Flanked Diketopyrrolopyrrole Derivative: A Solution-Processable Building Block for π-Conjugated Supramolecular Polymers

ABSTRACTWe have developed a highly modular electrostatically-mediated approach to colloid-colloid and polymer-colloid networks using ‘building block’ and ‘bricks and mortar’ self-assembly methodologies, respectively. The former approach involved functionalization of one type of nanoparticle building block with a primary amine and a counterpart building block with a carboxylic acid derivative. After combining these two systems, acid-base chemistry followed by immediate charge-pairing resulted in the spontaneous formation of electrostatically-bound mixed-nanoparticle constructs. The shape and size of these ensembles were controlled via variation of particle size and stoichiometries. In the ‘bricks and mortar’ approach, a functionalized polymer is combined with complementary nanoparticles to provide mixed polymer-nanoparticle networked structures. A notable feature is the inherent porosity resulting from the electrostatic assembly. The shape and size of these ensembles were controlled via variation of particle size, stoichiometries and the order in which they were added.

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Living supramolecular polymerization of fluorinated cyclohexanes

Nature Communications ◽

10.1038/s41467-021-23370-y ◽

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.

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Self-Assembly of Goldberg Polyhedra from a Concave [WV5O11(RCO2)5(SO4)]3–Building Block with 5-Fold Symmetry

Journal of the American Chemical Society ◽

10.1021/jacs.8b10866 ◽

2018 ◽

Vol 140 (50) ◽

pp. 17365-17368 ◽

Cited By ~ 39

Author(s):

Yuteng Zhang ◽

Hongmei Gan ◽

Chao Qin ◽

Xinlong Wang ◽

Zhongmin Su ◽

...

Keyword(s):

Self Assembly ◽

Building Block

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Halide ion-driven self-assembly of Zn(ii) compounds derived from an asymmetrical hydrazone building block: a combined experimental and theoretical study

New Journal of Chemistry ◽

10.1039/c6nj01534d ◽

2016 ◽

Vol 40 (12) ◽

pp. 10116-10126 ◽

Cited By ~ 9

Author(s):

Ghodrat Mahmoudi ◽

Farhad Akbari Afkhami ◽

Himanshu Sekhar Jena ◽

Parisa Nematollahi ◽

Mehdi D. Esrafili ◽

...

Keyword(s):

Self Assembly ◽

Building Block ◽

Theoretical Study ◽

Counter Ion ◽

Non Covalent Interactions ◽

Covalent Interactions

Self-assembly of Zn(ii) compounds is influenced by a counter ion and non-covalent interactions.

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

Nature Communications ◽

10.1038/s41467-021-27831-2 ◽

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.

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Crystal engineered acid-base complexes with 2d and 3d hydrogen bonding systems using p-hydroxybenzoic acid as the building block

Journal of the Serbian Chemical Society ◽

10.2298/jsc090416011z ◽

2010 ◽

Vol 75 (4) ◽

pp. 459-473 ◽

Cited By ~ 8

Author(s):

Pu Zhao ◽

Xian Wang ◽

Fang Jian ◽

Jun Zhang ◽

Lian Xiao

Keyword(s):

Self Assembly ◽

Building Block ◽

Three Dimensional ◽

Hydroxybenzoic Acid ◽

Acid Base ◽

3D Network ◽

Acid And Base ◽

Butyl Amine ◽

Bonding Systems ◽

Simply Connected

p-Hydroxybenzoic acid (p-HOBA) was selected as the building block for self-assembly with five bases, i.e., diethylamine, tert-butyl amine, cyclohexylamine, imidazole and piperazine, and generate the corresponding acid-base complexes 1-5. Crystal structure analyses suggest that proton-transfer from the carboxyl hydrogen to the nitrogen atom of the bases can be observed in 1-4; while only in 5 does a solvent water molecule co-exists with p-HOBA and piperazine. With the presence of O-H?O hydrogen bonds in 1-4, the deprotonated p-hydroxybenzoate anions (p-HOBAA-) are simply connected each other in a head-to-tail motif to form one-dimensional (1D) arrays, which are further extended to distinct two-dimensional (2D) (for 1 and 4) and three-dimensional (3D) (for 2 and 3 ) networks via N-H?O interactions. While in 5, neutral acid and base are combined pair wise by O-H?N and N-H?O bonds to form a 1D tape and then the 1D tapes are sequentially combined by water molecules to create a 3D network. Some interlayer or intralayer C-H?O, C-H?? and ??? interactions help to stabilize the supramolecular buildings. Melting point determination analyses indicate that the five acidbase complexes are not the ordinary superposition of the reactants and they are more stable than the original reactants.

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