Title: Azobenzene-based organic salts with ionic liquid and liquid crystalline properties

Abstract

Two sets of new azobenzene-based bromide salts are synthesized, and their thermal photochromic properties are studied. Both sets are based on the imidazolium cation. The first set (1) features a symmetric biscation where two imidazolium head groups (Im) with different alkyl chains (Cn) are connected to a central azobenzene unit (Azo): [Azo(C1-Im-Cn)₂]; n = 6, 8, 10, 12, 14. The other one contains an n-alkyl-imidazolium cation (Cn-Im) bearing a terminal azobenzene unit (C1-Azo) substituted with an alkoxy chain (O-Cm) of either two (2) or six (3) carbon atoms: [C1-Azo-O-Cm-Im-Cn]; m = 2, n = 8, 10, 12 and m = 6, n = 8, 10, 12, 14, 16. For both cation classes, the influence of alkyl chains of varying length on the thermal phase behavior was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). For five compounds (Azo(-C1-Im-C12)₂ (1d), Azo(-C1-Im-C12)₂ (1e), C1-Azo-O-C2-Im-C10 (2b), C1-Azo-O-C2-Im-C12 (2c), and C1-Azo-O-C6-Im-C16 (3e)), the formation of a liquid crystalline phase was observed. The biscationic salts (1) are all comparatively high melting organic salts (180–240 °C), and only the two representatives with long alkylchains (C12 and C14) exhibit liquid crystallinity. The monocationic salts with an O–C2 bridge (2) melt between 140 and 170more » °C depending on the alkyl chain length, but from an alkyl chain of 10 and more carbon atoms on they form a smectic A liquid crystalline phase. The representatives of the third set with a O–C6 bridge qualify as ionic liquids with melting points less than 100 °C. However, only the representative with a hexadecyl chain forms a liquid crystalline phase. Representative single crystals for all sets of cations could be grown that allowed for single crystal structure analysis. Together with small-angle X-ray scattering experiments they allow for a more detailed understanding of the thermal properties. As a result, through irradiation with UV-light (320–366 nm) all compounds undergo trans–cis isomerization, which reverses under visible light (440 nm).« less

Authors:

Stappert, Kathrin ^[1]; Muthmann, Johanna ^[1]; Spielberg, Eike T. ^[2]; Mudring, Anja -Verena ^[3]

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+ Show Author Affiliations

1. Ruhr-Univ. Bochum, Bochum (Germany)
2. Ruhr-Univ. Bochum, Bochum (Germany); Univ. Duisburg Essen, Essen (Germany)
3. Ruhr-Univ. Bochum, Bochum (Germany); Univ. Duisburg Essen, Essen (Germany); Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)

Publication Date:

Thu Jul 23 00:00:00 EDT 2015

Research Org.:

Ames Lab., Ames, IA (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1239153

Report Number(s):

IS-J-8786
Journal ID: ISSN 1528-7483

Grant/Contract Number:  

AC02-07CH11358

Resource Type:

Journal Article: Accepted Manuscript

Journal Name:

Crystal Growth and Design

Additional Journal Information:

Journal Volume: 15; Journal Issue: 9; Journal ID: ISSN 1528-7483

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY