Aromatic bent-core liquid crystals : an opportunity for introducing terdentate binding units into mesophases

Nozary, Homayoun; Rivera, Jean-Pierre; Tissot, Paul; Piguet, Claude; Morgantini, Pierre-Yves; Weber, Jacques; Bernardinelli, Gérald Hugues; Bünzli, Jean-Claude G.; Deschenaux, Robert; Donnio, Bertrand; Guillon, Daniel

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Title		Aromatic bent-core liquid crystals : an opportunity for introducing terdentate binding units into mesophases
Authors		Nozary, Homayoun Rivera, Jean-Pierre Tissot, Paul Piguet, Claude Morgantini, Pierre-Yves Weber, Jacques Bernardinelli, Gérald Hugues Bünzli, Jean-Claude G. Deschenaux, Robert Donnio, Bertrand Guillon, Daniel show all authors [1 - 11]
Published in		Chemistry of Materials. 2002, vol. 14, no. 3, p. 1075-1090
Abstract		Lipophilic linear semirigid side arms containing two or three successive phenyl rings separated by carboxylate spacers have been connected to the 5 or 6 positions of bent aromatic terdentate 2,6-bis(benzimidazol-2-yl)pyridine binding units to give extended V-shaped (L11) and I-shaped receptors (L12, L12b, and L13). The carboxylate spacers limit the flexibility of the side arms and provide crossed arrangements of the successive aromatic rings in the crystal structure of L12b (C63H61N5O10; triclinic, P, Z = 2) in agreement with semiempirical calculations performed on optimized gas-phase geometries. Moreover, the carboxylate spacers in L11−L13 prevent efficient electronic delocalization between the connected aromatic rings and act as weak π acceptors producing a slight increase of the energy of the 1ππ* and 3ππ* levels centered on the terdentate binding unit. Intermolecular π-stacking interactions observed in the crystal of L12b are invoked to rationalize (i) the peculiar excimer emission of L11 in the solid state and (ii) the rich and varied calamitic (I-shaped L12, L12b, and L13) and columnar (V-shaped L11) mesomorphism observed at high temperature. The ColR mesophase detected for L11 demonstrates that V-shaped bent terdentate binding units are compatible with liquid-crystalline behavior. Complexation of L11 with lanthanide(III) produces I-shaped complexes [Ln(L11)(NO3)3] (Ln = La, Eu, Gd, Tb, and Lu) possessing a large axial anisometry as found in the crystal structure of [Lu(L11)(CF3CO2)3(H2O)] (LuC81H87N5O17F9; triclinic, P, Z = 2), which exists in the solid state as H-bonded dimers. No mesomorphism is detected for the complexes as a result of the large perpendicular expansion brought by the metallic coordination site, but the high energy of the ligand-centered 3ππ* prevents Eu(5D0) → L11 back transfer in the Eu(III) complex, which thus exhibits sizable red luminescence at room temperature, a crucial point for the design of luminescent materials.
Identifiers		DOI: 10.1021/cm011162c
Full text		Article (Published version) (286 Kb) - Limited access to UNIGE Other version: http://pubs.acs.org/doi/abs/10.1021/cm011162c
Structures		Faculté des sciences / Section de chimie et biochimie / Département de chimie physique
Research group		Groupe Weber
Citation (ISO format)		NOZARY, Homayoun et al. Aromatic bent-core liquid crystals : an opportunity for introducing terdentate binding units into mesophases. In: Chemistry of Materials, 2002, vol. 14, n° 3, p. 1075-1090. https://archive-ouverte.unige.ch/unige:3222