Controlled supramolecular polymerization of π-systems

Ghosh, Goutam; Dey, Pradip; Ghosh, Suhrit

doi:10.1039/d0cc02787a

Cited by 94 publications

(63 citation statements)

References 104 publications

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“…Many recent examples of LSP are based on a similar use of offpathway aggregates 14 , which can be self-assembled from diverse building blocks such as rylene dyes [15][16][17][18][19][20][21] , (aza)-BODIPY dyes 22,23 , N-heteroangulenes 24 and amphiphilic Pt II complexes 25 . Further examples make use of the counter-anion modulated aggregation of Pt II and Pd II pincer-type complexes 26 , the coupling of SP with a chemical fuel or light [27][28][29][30] , the trapping of an active monomer using "dummy" monomers incapable of 1D supramolecular polymerization 31 and the amplification of macrocycles from dynamic combinatorial libraries 32 .…”

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confidence: 99%

Living supramolecular polymerization of fluorinated cyclohexanes

et al. 2021

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The 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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confidence: 99%

Living supramolecular polymerization of fluorinated cyclohexanes

et al. 2021

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“…While this research relied for many years on thermodynamic control [11][12][13][14] , i.e. the generation of equilibrium structures, only recently an advancement towards kinetically controlled supramolecular polymerization processes [15][16][17][18][19][20][21] and the smart utilization of out-of-equilibrium species took place [22][23][24] . Thus combining knowledge on the thermodynamics with detailed kinetic analysis enabled the control of supramolecular polymerization pathways towards certain supramolecular architectures [25][26][27] .…”

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confidence: 99%

Control of self-assembly pathways toward conglomerate and racemic supramolecular polymers

et al. 2020

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Homo- and heterochiral aggregation during crystallization of organic molecules has significance both for fundamental questions related to the origin of life as well as for the separation of homochiral compounds from their racemates in industrial processes. Herein, we analyse these phenomena at the lowest level of hierarchy – that is the self-assembly of a racemic mixture of (R,R)- and (S,S)-PBI into 1D supramolecular polymers. By a combination of UV/vis and NMR spectroscopy as well as atomic force microscopy, we demonstrate that homochiral aggregation of the racemic mixture leads to the formation of two types of supramolecular conglomerates under kinetic control, while under thermodynamic control heterochiral aggregation is preferred, affording a racemic supramolecular polymer. FT-IR spectroscopy and quantum-chemical calculations reveal unique packing arrangements and hydrogen-bonding patterns within these supramolecular polymers. Time-, concentration- and temperature-dependent UV/vis experiments provide further insights into the kinetic and thermodynamic control of the conglomerate and racemic supramolecular polymer formation.

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“…Supramolecular polymers present us with a broad blueprint to struggle for the new generation of functional materials such as soft matter electronics, drug delivery, and catalysts in a relatively simple way 1 – 7 . Especially, the emergence of the living supramolecular polymerization (LSP) method provides an exciting and novel research avenue, which has been applied to establish supramolecular polymers with efficient modulating and uniformity of chain growth and dispersity 8 , 9 . To call a “living”, in the strict sense, the growth of supramolecular polymers from the active ends should be demonstrated by multicycle experiments 10 – 14 .…”

Section: Introductionmentioning

confidence: 99%

Oriented arrangement of simple monomers enabled by confinement: towards living supramolecular polymerization

Zong

Shi

et al. 2021

Nat Commun

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The 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.

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Controlled supramolecular polymerization of π-systems

Abstract: Externally-initiated controlled supramolecular polymerization of the kinetically trapped aggregated state in a chain growth mechanism can produce well-defined living supramolecular polymers and copolymers.

Cited by 94 publications

References 104 publications

Living supramolecular polymerization of fluorinated cyclohexanes

Living supramolecular polymerization of fluorinated cyclohexanes

Control of self-assembly pathways toward conglomerate and racemic supramolecular polymers

Oriented arrangement of simple monomers enabled by confinement: towards living supramolecular polymerization

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