In this review, we describe the recent advances in supramolecular helical assemblies formed from chiral and achiral small molecules, oligomers (foldamers), and helical and nonhelical polymers from the viewpoints of their formations with unique chiral phenomena, such as amplification of chirality during the dynamic helically assembled processes, properties, and specific functionalities, some of which have not been observed in or achieved by biological systems. In addition, a brief historical overview of the helical assemblies of small molecules and remarkable progress in the synthesis of single-stranded and multistranded helical foldamers and polymers, their properties, structures, and functions, mainly since 2009, will also be described.

Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions

Polycyclic Hydrocarbons Vol. 1. Pp. xxvi + 487. 126S. (With a chapter on carcinogenesis by Regina Schoental.) Vol. 2. Pp. lvii + 487. 140s. By E. Clar. (London and New York: Academic Press; Berlin: Springer-Verlag, 1964.)

Polycyclic Aromatic Hydrocarbons

Discotic Liquid Crystals.

Light-driven phenomena both in living systems and nonliving materials have enabled truly fascinating and incredible dynamic architectures with terrific forms and functions. Recently, liquid crystalline materials endowed with photoresponsive capability have emerged as enticing systems. In this Review, we focus on the developments of light-driven liquid crystalline materials containing photochromic components over the past decade. Design and synthesis of photochromic liquid crystals (LCs), photoinduced phase transitions in LC, and photoalignment and photoorientation of LCs have been covered. Photomodulation of pitch, polarization, lattice constant and handedness inversion of chiral LCs is discussed. Light-driven phenomena and properties of liquid crystalline polymers, elastomers, and networks have also been analyzed. The applications of photoinduced phase transitions, photoalignment, photomodulation of chiral LCs, and photomobile polymers have been highlighted wherever appropriate. The combination of photoc...

Light-Driven Liquid Crystalline Materials: From Photo-Induced Phase Transitions and Property Modulations to Applications.

This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions.

Ionic Liquid Crystals: Versatile Materials.

A series of guanidinium salts 1(C n ) m –4(C n ) m  X bearing phenyl alkoxybenzoate cores have been synthesised and their mesomorphic properties have been investigated by polarising optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction experiments (small-angle X-ray scattering and wide-angle X-ray scattering). While compounds 1(C12)1 X and 3(C12)1 X with one alkoxy chain showed smectic A (SmA) phases irrespective of the counter ion, compounds 1(C12)2 OTf and 3(C12)2 OTf with two alkoxy chains displayed SmA phases and the corresponding chlorides 1(C12)2 Cl and 3(C12)2 Cl displayed Colh. Guanidinium salts 1(C n )3–4(C n )3 X with three alkoxy chains showed Colh phases. Whereas the use of cyclic guanidinium head groups rather than acyclic ones had only a minor influence on the mesophase properties, melting points were significantly decreased by bent core units instead of linear core units. Replacement of chloride counterions by triflate lead to a further depression of...

Liquid crystalline guanidinium phenylalkoxybenzoates: towards room temperature liquid crystals via bending of the mesogenic core and the use of triflate counter ions

Ionic liquid crystals based on congruent ion pairs composed of mesogenic cations and anions of similar shape provide an attractive tool for the tuning of mesophase properties. Here, the effect of the number and symmetry of lipophilic side chains and the type of head group on the phase type and thermal mesophase properties was probed by the synthesis and investigation of two series of novel guanidinium and imidazolium sulphonates and compared with the corresponding iodides. Their mesomorphic properties were examined via differential scanning calorimetry, optical polarising microscopy and X-ray diffraction. While derivatives bearing only one alkoxy chain in either cation or anion with up to three alkoxy chains in total within the ion pairs display smectic A mesophases, hexagonal columnar mesophases were observed for all other compounds with four or five alkoxy chains totally irrespective of the head group. However, with increasing steric bulk, i.e. with a total of six alkoxy chains, the symmetry of the aryl...

Headgroups versus symmetry in congruent ion pairs: which one does the job in mesomorphic aryl guanidinium and aryl imidazolium sulphonates?

A series of ionic liquid crystals with an alkoxy biphenyl unit tethered via an alkyl spacer to a guanidinium head group were synthesised and the mesomorphic properties were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction (XRD; WAXS and SAXS). Whereas all symmetrical guanidinium chlorides with the same chain lengths in alkyl tail and spacer displayed enantiotropic SmA2 phases, monotropic SmC2 phases with 1–2 K temperature range were only formed for chain lengths ≥ C10. Shifting the calamitic core more closely to the ionic head group by decreasing the tether length and simultaneously increasing the terminal alkyl chain improved the stability of both SmA and SmC phases considerably and led to enantiotropic SmC phases for the guanidinium chloride with C14 alkyl tail and C6 spacer. An even more pronounced effect was detected during anion exchange. Bromide, iodide, hexafluorophosphate, thiocyanate and triflate suppressed any SmC phase, whereas tetrafluor...

Induction of ionic smectic C phases: a systematic study of alkyl-linked guanidinium-based liquid crystals

A small series of dendrimers consisting of a star-shaped triphenylbenzene core unit and bulky lateral groups was synthesised and their mesomorphic properties were investigated via differential scan...

Johannes Christian Haenle

Papers

Discotic Liquid Crystals.

Liquid crystalline guanidinium phenylalkoxybenzoates: towards room temperature liquid crystals via bending of the mesogenic core and the use of triflate counter ions

Headgroups versus symmetry in congruent ion pairs: which one does the job in mesomorphic aryl guanidinium and aryl imidazolium sulphonates?

Induction of ionic smectic C phases: a systematic study of alkyl-linked guanidinium-based liquid crystals

Dendrimeric triphenylbenzenes: helical versus zig-zag arrangement in columnar mesophases