Supramolecular dendrimers: Unusual mesophases of ionic liquid crystals derived from protonation of DAB dendrimers with facial amphiphilic carboxylic acids

Cook, A.G.; Baumeister, Ute; Tschierske, Carsten

doi:10.1039/b415892j

Cited by 96 publications

(49 citation statements)

References 101 publications

(42 reference statements)

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“…38 Using the calculated propagators, the volume fractions and single-molecule partition functions are evaluated. The W A , W B , W C , and P fields are subsequently relaxed using various convergence schemes 26,39,40 in order to satisfy the remaining SCFT equations, (eqs [16][17][18][19]. We also minimize the free energy density with respect to the volume and shape of the periodic simulation box with a variable cell shape method.…”

Section: Summary and Discussionmentioning

confidence: 99%

“…We employ a numerical solution of the SCFT equations (eq [13][14][15][16][17][18][19] to evaluate the canonical ensemble free energies for various candidate inhomogeneous phases in their unit cells. Initial field configurations are seeded in order to produce a unit cell of a given mesophase, and the modified diffusion equation (eq 9) is solved pseudospectrally with an operator splitting scheme.…”

Section: Summary and Discussionmentioning

confidence: 99%

“…Block copolymers of different architectures, such as ABC triblock copolymers, 11 supramolecular blends of AB and B′C diblock copolymers, 12 T-shaped rod-coil chains [13][14][15][16] and dendronized polymers [17][18][19][20] form other, more desirable twodimensional morphologies than the hexagonal lattice of the simple AB diblock. For example, T-shaped rod-coil polymers, such as those studied by Tschierske et al, assemble into several two-dimensional phases, and these include two cubic phases: square and rectangular packed cylinders, as well as the hexagonal phase.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Novel Phase Morphologies in a Microphase-Separated Dendritic Polymer Melt

Lee¹,

Elliott²,

Mezzenga³

et al. 2009

Macromolecules

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Equilibrium phase morphologies of two different dendritic block copolymer melts are calculated and compared. These copolymers have a pitchfork-like architecture and consist of three distinct blocks that correspond roughly to the handle, the connecting middle dendron structure, and the attached tines of a pitchfork. The first melt considered consists of a copolymer that has a simple Y-junction middle block, and it connects the handle to two tines. The second is similar except its dendritic middle block branches twice to connect to four tines. Polymeric segments are modeled as flexible Gaussian threads and interactions between dissimilar blocks are all contact-like, Flory-Huggins repulsions. All calculations are done for incompressible melts in the context of self-consistent mean-field theory. We find that several morphologies compete for stability depending on the architecture and lengths of the blocks as well as their incompatibilities. As many as four stable two-dimensional phases appear in the phase diagram including: columnar square, rectangular and hexagonally packed structures. A long handle and a moderate length of the dendron are essential for stabilizing the square phases, and the four tine copolymer shows a larger region of stability for these phases compared to the Y-junction middle block system. A remarkable continuous phase transition between the square and rectangular phases is also found and investigated.

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Section: Summary and Discussionmentioning

confidence: 99%

Section: Summary and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Novel Phase Morphologies in a Microphase-Separated Dendritic Polymer Melt

Lee¹,

Elliott²,

Mezzenga³

et al. 2009

Macromolecules

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“…The ion-bonded star supramolecule, HDTP/DMP, was prepared following a method similar to the one described by Cook et al [18] for the synthesis of ionic dendrimers (Scheme 1). Ionic bonds formed from the interaction of tertiary amino groups in HDTP with carboxyl group in DMP.…”

Section: Synthesis and Characterization Of Ion-bonded Star Supramoleculementioning

confidence: 99%

A Strategy for Synthesis of Ion‐Bonded Supramolecular Star Polymers by Reversible Addition‐Fragmentation Chain Transfer (RAFT) Polymerization

Tao

Bai

et al. 2008

Macromol. Rapid Commun.

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We have developed a novel strategy for the preparation of ion‐bonded supramolecular star polymers by RAFT polymerization. An ion‐bonded star supramolecule with six functional groups was prepared from a triphenylene derivative containing tertiary amino groups and trithiocarbonate carboxylic acid, and used as the RAFT agent in polymerizations of tert‐butyl acrylate (tBA) and styrene (St). Molecular weights and structures of the polymers were characterized by 1H NMR and GPC. The results show that the polymerization possesses the character of living free‐radical polymerization and the ion‐bonded supramolecular star polymers PSt, PtBA, and PSt‐b‐PtBA, with six well‐defined arms, were successfully synthesized.magnified image

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“…It is interesting to note that besides the T-shaped polyphiles shown in figure 7a, there are also T-shaped polyphiles with a reversed position of hydrophilic and lipophilic units [45][46][47][48][49][50][51] as shown in figure 7b. These compounds also form polygonal cylinder phases with cells ranging from triangular to hexagonal [32].…”

Section: Liquid Crystal Honeycombsmentioning

confidence: 99%

Complex tiling patterns in liquid crystals

et al. 2011

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In this account recent progress in enhancing the complexity of liquid crystal self-assembly is highlighted. The discussed superstructures are formed mainly by polyphilic T-shaped and X-shaped molecules composed of a rod-like core, tethered with glycerol units at both ends and flexible non-polar chain(s) in lateral position, but also related inverted molecular structures are considered. A series of honeycomb phases composed of polygonal cylinders ranging from triangular to hexagonal, followed by giant cylinder honeycombs is observed for ternary T-shaped polyphiles on increasing the size of the lateral chain(s). Increasing the chain size further leads to new modes of lamellar organization followed by three-dimensional and two-dimensional structures incorporating branched and non-branched axial rod-bundles. Grafting incompatible chains to opposite sides of the rod-like core leads to quaternary X-shaped polyphiles. These form liquid crystalline honeycombs where different cells are filled with different material. Projected on an Euclidian plane, all honeycomb phases can be described either by uniformly coloured Archimedean and Laves tiling patterns (T-shaped polyphiles) or as multi-colour tiling patterns (X-shaped polyphiles). It is shown that geometric frustration, combined with the tendency to segregate incompatible chains into different compartments and the need to find a periodic tiling pattern, leads to a significant increase in the complexity of soft self-assembly. Mixing of different chains greatly enhances the number of possible 'colours' and in this way, periodic structures comprising up to seven distinct compartments can be generated. Relations to biological self-assembly are discussed shortly.

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Supramolecular dendrimers: Unusual mesophases of ionic liquid crystals derived from protonation of DAB dendrimers with facial amphiphilic carboxylic acids

Cited by 96 publications

References 101 publications

Novel Phase Morphologies in a Microphase-Separated Dendritic Polymer Melt

Novel Phase Morphologies in a Microphase-Separated Dendritic Polymer Melt

A Strategy for Synthesis of Ion‐Bonded Supramolecular Star Polymers by Reversible Addition‐Fragmentation Chain Transfer (RAFT) Polymerization

Complex tiling patterns in liquid crystals

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