Tuning liquid crystalline phase behaviour in columnar crown ethers by sulfur substituents

Kirres, Jochen; Schmitt, Katharina; Wurzbach, Iris; Gießelmann, Frank; Ludwigs, Sabine; Ringenberg, Mark R.; Ruff, Adrian; Baro, Angelika

doi:10.1039/c7qo00077d

Cited by 12 publications

(10 citation statements)

References 95 publications

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“…Differences between these ligands rely on the nature of atoms linking the o ‐terphenylphenyl moieties to the dodecyl side chains. Indeed, some of us showed recently that using sulfur atoms instead of oxygen atoms modify significantly the ligand's liquid crystalline phase stability . Replacing oxygen by the bulkier sulfur led to decreased LC‐to‐isotropic state transition temperatures (clearing temperatures) and increased mesophase range, presumably due to a less tight intracolumnar packing but improved nanoseggregation.…”

Section: Figurementioning

confidence: 99%

“…LC properties were studied by polarized optical microscopy (POM, Figures S2–S4) differential scanning calorimetry (DSC, Figures S5–S7), and wide and small angle X‐ray scattering (WAXS and SAXS, see Supporting Information Figures S8–S13 for diffractograms). Thermodynamic data, mesophase identification and parameters are gathered in Table , together with the ligand precursors for comparison . All complexes show an enantiotropic hexagonal columnar mesophase whose temperature range is enhanced as compared to the pure ligand.…”

Section: Figurementioning

confidence: 99%

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Lord of The Crowns: A New Precious in the Kingdom of Clustomesogens

et al. 2018

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Replacing pure inorganic materials by functional organic-inorganic hybrid ones to lower production costs has become a major challenge, in particular for the optoelectronic industry. Adding nanostructuration abilities meanwhile preserving homogeneity is even more challenging for this class of new materials. Here we show that red-NIR emissive ternary molybdenum cluster salts can be assembled to liquid crystalline 15C5 crown ethers. The resulting hybrids are homogeneous and stable up to high temperature despite the weakness of the supramolecular interactions binding both components. These are illustrated by Cs MAS NMR. All hybrids show hexagonal columnar arrangements and strong red-NIR emission. Surprisingly, when chlorinated clusters are used instead of brominated ones, the mesophase stability is largely enhanced.

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Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Lord of The Crowns: A New Precious in the Kingdom of Clustomesogens

et al. 2018

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“…For methylimidazolium ILCs the emergence of mesomorphic properties via the sulfur motif was reported [10] . Stabilization of mesophases was also found for columnar palladium complexes with dipicolinic acid‐derived pincer ligands [11] and columnar crown ethers carrying thioethers instead of alkoxy side chains [12] . Furthermore, the S/O replacement led to a higher degree of order in columnar mesophases of 6‐oxoverdazyl radicals [13] .…”

Section: Introductionmentioning

confidence: 88%

Chasing Self‐Assembly of Thioether‐Substituted Flavylium Salts in Solution and Bulk State

et al. 2022

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Dedicated to Professor Herbert Mayr on the occasion of his 75th birthdayTwo series of flavylium triflates carrying alkoxy side chains in the A-ring (benzo unit of chromylium salt) and thioethers in the B ring (phenyl unit) (O n -Fla-S m ) as well as thioethers at both A and B ring (S n -Fla-S m ) were synthesized in order to understand the effect of thioether functionalization on their self-assembly and electronic properties. Concentration-dependent and diffusion ordered (DOSY) NMR experiments of O 1 -iV-Fla-S 3 indicate the formation of columnar H-aggregates in solution with antiparallel intracolumnar stacking of the AC unit (chromylium) of the flavylium triflate, in agreement with the solid state structure of O 1 -V-Fla-S 1 . Thioether substitution on the B ring changes the linear optical properties in solution, whereas it has no effect on the A ring. According to differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction bulk self-assembly of these ionic liquid crystals (ILCs) depends on the total number of side chains, yielding SmA and Lam Col phases for ILCs with 2-3 chains and Col ro , Col h phases for ILCs with 3-6 chains. Thus, we demonstrated that thioethers are a useful design tool for ILCs with tailored properties.

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“…Indeed, some of us showed recently that using sulfur atoms instead of oxygen atoms modify significantly the ligand's liquid crystalline phase stability. [20] Replacing oxygen by the bulkier sulfur led to decreased LC-to-isotropic state transition temperatures (clearing temperatures) and increased mesophase range, presumably due to a less tight intracolumnar packing but improved nanoseggregation. We could then expect the same effect for our complexes.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…Thermodynamic data, mesophase identification and parameters are gathered in Table 1, together with the ligand precursors for comparison. [20,23] All complexes show an enantiotropic hexagonal columnar mesophase whose temperature range is enhanced as compared to the pure ligand. This phenomenon was already observed when a larger 18C6 crown ether was used instead of 15C5 and is attributed to the cluster polyionicity that insure a better stability of the supramolecular assemblies upon heating.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

Lord of The Crowns: A New Precious in the Kingdom of Clustomesogens

et al. 2018

Self Cite

View full text Add to dashboard Cite

Replacing pure inorganic materials by functional organicinorganic hybrid ones to lower production costs has become a major challenge, in particular for the optoelectronic industry. Adding nanostructuration abilities meanwhile preserving homogeneity is even more challenging for this class of new materials. Here we show that Red-NIR emissive ternary molybdenum cluster salts can be assembled to liquid crystalline 15C5 crown ethers. The resulting hybrids are homogeneous and stable up to high temperature despite the weakness of the supramolecular interactions binding both components. These are illustrated by 133 Cs MAS NMR. All hybrids show hexagonal columnar arrangements and strong Red-NIR emission. Surprisingly, when chlorinated clusters are used instead of brominated ones, the mesophase stability is largely enhanced.

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Tuning liquid crystalline phase behaviour in columnar crown ethers by sulfur substituents

Abstract: Sulfur-containing side chains in the periphery ofo-terphenyl or triphenylene units of crown ethers induce room-temperature columnar mesophases.

Cited by 12 publications

References 95 publications

Lord of The Crowns: A New Precious in the Kingdom of Clustomesogens

Lord of The Crowns: A New Precious in the Kingdom of Clustomesogens

Chasing Self‐Assembly of Thioether‐Substituted Flavylium Salts in Solution and Bulk State

Lord of The Crowns: A New Precious in the Kingdom of Clustomesogens

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