Pathway Complexity in π-Conjugated Materials

Korevaar, Peter A.; Greef, Tom F. A. de; Meijer, E. W.

doi:10.1021/cm4021172

Cited by 247 publications

(228 citation statements)

References 78 publications

Supporting

Mentioning

219

Contrasting

Unclassified

Order By: Relevance

“…36 De Greef, Meijer and coworkers lead the pioneering work in the thermodynamic and kinetic elucidation of small molecule based self-assembly pathways in supramolecular polymers. 33,424,427 A nucleus that has a higher free energy compared to the monomeric species and the significant energy barrier for selfassembly result in characteristic lag phases in the polymerization kinetics, in full agreement with protein aggregation systems. [428][429][430][431][432][433][434] Detailed studies have highlighted the presence of these lag phases, as well as the presence of competing offpathway aggregates, which can act as traps for free monomer and are thereby able to buffer the assembly dynamics.…”

Section: Highlightmentioning

confidence: 53%

Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

122

102

View full text Add to dashboard Cite

The self-assembly into supramolecular polymers is a process driven by reversible non-covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli-responsive properties: (1) endcapping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of selfassembly kinetics of synthetic supramolecular systems. V C 2016

show abstract

Section: Highlightmentioning

confidence: 53%

Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

122

102

View full text Add to dashboard Cite

show abstract

“…The observed evolution of aggregation is consistent with the model of homogeneous nucleated growth of nanofibers driven by π−π stacking. 35,36 As evidenced by POM (Figure 2a), a capillary filled with freshly prepared (day 0) P3HT/TCB solution appeared isotropic. However, capillaries filled with solutions that had remained in the vial for 2 or more days prior to filling appeared birefringent when viewed through crossed polarizers on the same day they were filled, and these capillaries appeared increasingly bright up to day 36 ( Figure 2a).…”

Section: Resultsmentioning

confidence: 95%

Liquid Crystalline Poly(3-hexylthiophene) Solutions Revisited: Role of Time-Dependent Self-Assembly

Kleinhenz¹,

Rosu²,

Chatterjee

et al. 2015

Chem. Mater.

101

View full text Add to dashboard Cite

Poly(3-hexylthiophene) (P3HT) in trichlorobenzene solution self-assembles and exhibits liquid crystal ordering when confined to rectangular capillaries. The relative proportion of polymer assemblies increases with time, as determined by UV−vis spectroscopic analysis. Polarized optical microscopy (POM) reveals development of birefringence and monodomainlike long-range ordering. Micro-Raman spectroscopy was used to calculate the orientational order parameters, ⟨P 2 ⟩ and ⟨P 4 ⟩, of the liquid-crystalline P3HT solutions. The order parameter ⟨P 2 ⟩ increased with time up to 0.35, indicating increased anisotropy. The calculated depolarization ratio (ρ v ) from depolarized dynamic light scattering measurements points to the time-dependent formation of highly ordered P3HT nanostructures, whereas cryogenic transmission electron microscopy was employed for the direct visualization of the rodlike assemblies. POM shows that the observed anisotropy can be preserved in P3HT films drawn from aged solutions. These results suggest that P3HT self-assembly leads to a liquid-crystalline solution of conjugated polymer aggregates, which may lead to a viable approach for optimization of processes for organic electronic device applications. Such ordered and oriented conjugated polymer assemblies have many desirable attributes for high-performance device applications, where the ability to control nanothrough macroscale molecular ordering is required.

show abstract

“…[5][6][7][8][9][10][11][12][13][14][15][16][17] In order to achieve these functionalities, highlyordered, adaptive nanostructures formed via a cooperative supramolecular polymerization mechanism are highly desirable. 18 The introduction of orthogonal noncovalent interactions, 19 from which hydrogen bonding and combinations with other secondary interactions are by far the most exploited ones, 20 represents a rational means for this purpose.…”

Section: Introductionmentioning

confidence: 99%