New chiral discotics with helical organization of the mesophase—liquid crystalline derivatives of dibenzotetraaza[14]annulene

• Published in: Tetrahedron Vol. 68; no. 20; pp. 3875 - 3884
• Main Authors: Grolik, Jarosław, Dudek, Łukasz, Eilmes, Julita, Eilmes, Andrzej, Górecki, Marcin, Frelek, Jadwiga, Heinrich, Benoît, Donnio, Bertrand
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 20.05.2012; Elsevier
• Subjects: Chemistry; Chemistry, Organic; Cross-disciplinary physics: materials science; rheology; Derivatives; Dibenzotetraazaannulene; Differential scanning calorimetry; ECD spectroscopy; Electronics; Exact sciences and technology; Helical; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Liquid crystals; Materials science; Mesophase; Methods of nanofabrication; Molecular Dynamics; Organic chemistry; Organizations; Phases; Physical Sciences; Physics; Preparations and properties; Quantum chemistry; SA-XRD; Science & Technology; Supramolecular and biochemical assembly; Supramolecular chirality; SA-XRD; Molecular Dynamics; Dibenzotetraazaannulene; ECD spectroscopy; Liquid crystals; Supramolecular chirality; POLYMERS; HEXA-PERI-HEXABENZOCORONENES; CHARGE-CARRIER MOBILITY; BEHAVIOR; SELF-ORGANIZATION; MOLECULES; TRANSPORT; PHASE; METALLOMESOGENS; COLUMNAR MESOPHASE; Chemical analysis; Quantum chemistry; Molecular structure; Nitrogen heterocycle; Molecular dynamics method; Carbon Isotopes; Molecular dynamics; Chiral compound; XRD; High temperature; Electrospray; Optical microscopy; Chirality; Supramolecular structure; Helical structure; Chemical synthesis; Carbon 13; Low temperature; Differential scanning calorimetry; Mesomorphism; Theoretical study; Mass spectroscopy; Smectic state; Discotic liquid crystals; Columnar structure; Circular dichroism; Planar molecule; Optical purity; Mesophases; NMR spectroscopy
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2012.03.037

Two optically pure derivatives of dibenzotetraaza[14]annulene, bearing four (S)- or (R)- 3,7-dimethyloctoxy peripheral chiral tails, respectively, and two hydroxybenzoyl meso substituents were synthesized using a convergent multi-step route. The structure of the products was determined by 1H and 13C NMR spectroscopy, ESI-MS, and elemental analysis. The mesomorphic behavior of the two chiral compounds, deciphered by differential scanning calorimetry (DSC), small-angle X-ray diffractometry (SA-XRD), and polarizing optical microscopy (POM) investigations, revealed the induction of two lamello-columnar phases, i.e., columnar stacks confined in smectic layers, whose columns may be arranged either according to the pg rectangular planar symmetry (for the low-temperature phase) or without registry between vicinal layers (for the high-temperature mesophase). Evidence of a helical organization of the molecules in the mesophases was obtained using a combination of electronic circular dichroism (ECD) and SA-XRD results, Molecular Dynamics simulations and quantum-chemical calculations. [Display omitted]