0000000000684367
AUTHOR
Thorsten Lifka
Comparison of Alkoxy-substituted 4,4´-Distyrylbiphenyls and the Corresponding 4,4´-Distyrylbenzenes
Abstract Configurationally highly pure (E,E)-4,4´-bis(styryl)biphenyls 2a - e were obtained by Siegrist reactions of 4,4´-dimethylbiphenyl 3 and alkoxy-substituted benzaldimines (4a - e). DSC measurements have indicated different crystalline modifications of these conjugated compounds. The stilbenoid chromophores of 2a - e are compared to the stilbenoid chromophores in the OPV series, which have a similar length of conjugation. The intense fluorescence and the high transparency in the visible region are promising properties for an application of the donor-substituted compounds 2a - e in twophoton absorption (TPA) techniques.
Mesomorphic Donor-Acceptor-substituted 1,4-Distyrylbenzenes
Conjugated oligomers with terminal donor-acceptor substitution attract increasing attention in organic chemistry because of their outstanding and not seldom unexpected properties in materials science [1 – 4]. Although a variety of oligo(1,4-phenylene-vinylene)s with terminal donor-acceptor substitution (DAOPVs 1, Scheme 1) are known [5 – 22], the number of thermotropic liquid crystals among them is very low and is confined to monomers (n = 1), that means to certain push-pull substituted (E)-stilbenes [23 – 31]. The behavior of conjugatedmolecules, which are highly polar and form mesophases by self-organization, is very interesting for various applications of liquid crystals [3]. A big disad…
3,6-Bis(2-arylethenyl)-1,2,4,5-tetrazine - Synthese, Fl�ssigkristallinit�t und Photochemie
3,6-Bis(2-arylethenyl)-1,2,4,5-tetrazines - Synthesis, LC Properties and Photochemistry The (E,E)-3,6-Bis(2-arylethenyl)-1,2,4,5-tetrazines 8 were prepared in a synthetic sequence starting with aromatic aldehydes 1 and cinnamic acids 2, respectively (Scheme 1). The rod-like conjugated molecules represent calamitic mesogens as well as extended chromophores. Hence, we investigated the formation of liquid crystals, achieved by the introduction of long flexible side chains, and the photochemical behaviour that is characterized by the fragmentation of the central ring (Scheme 3).
Photochemistry of 3,6-bis(styryl)pyridazines in solution and in neat liquid crystalline phase—optical switching and imaging techniques
Abstract 3,6-Bis(styryl)pyridazines 1a – f with 2–6 alkoxy groups show on irradiation in solution a stereoisomerization which leads to a photostationary state of ( E , E )- and ( E , Z )-isomer. Sensitizing and quenching experiments reveal that the ( E , E )→( E , Z ) route is a pure triplet process, whereas the ( E , Z )→( E , E ) route can have a minor singlet by-reaction. Hexyloxy or dodecyloxy chains on the terminal benzene rings convey the ( E , E )-isomers of compounds 1a , b , d – f thermotropic liquid crystalline properties. In particular S A , S C , and S F/I phases were studied with regard to their photochemical behavior. Depending on the system, photodegradation of the smectic ph…
Dodecyloxy-substituted 2,4,6-tris(styryl)pyridines
(E,E,E)-2,4,6-Tris(styryl)pyridines 2a-c with 3, 6 or 9 dodecyloxy substituents were prepared by the highly stereoselective condensation reaction of collidine (8) and the corresponding phenyl-(1-phenyl-methylidene)amines 7a-c (Siegrist reaction). In contrast to the corresponding compounds with a benzene or a 1,3,5-triazine core, 2a-c do not show any hints for the formation of thermotropic liquid crystals. The major application of such star-shaped systems is in the field of nonlinear optics.
Alkoxy substituted (E,E)-3,6-bis(styryl)pyridazine—a photosensitive mesogen for liquid crystals
Abstract (E,E)-3,6-Bis(styryl)pyridazines (3a–t) bearing 2, 4 or 6 alkoxy chains were prepared by applying the Siegrist reaction of 3,6-dimethylpyridazine (13) and the corresponding azomethines 10a–t. The transversal dipole moment of these calamitic compounds effects an extremely high tendency for self-organization in thermotropic LC phases (N, SA, SB, SC, SE, SI/F, and Cub). The conjugated core structure represents moreover a chromophore with a high photosensitivity for (E,E)⇄(E,Z) isomerization reactions: this property makes the compounds interesting for optical imaging and switching techniques.
(E,E,E)-4,4′-Distyrylstilbenes – Synthesis, Photophysics, Photochemistry and Phase Behavior
The fluorescence quantum yields F(n) of oligo[2,5-bis(propyloxy)-1,4-phenylenevinylene]s (1b) reach for the trimer (n = 3) in solution a maximum of 86 %, which is almost twice as high as for the monomer (n = 1) and the octamer or undecamer (n = 8, 11). The latter represent the convergence limit of 46 %. 4-Mono-, 3,4-di- or 3,4,5-trisubstituted terminal phenyl rings in the trimers 6a–f do not lead to calamitic or phasmidic liquid crystals; however, 2,3,4-trisubstitution with hexyloxy groups (6h) and even with OCH3 groups (6g) effects LC formation. Irradiation with energy-rich UV light provokes a crosslinking of the originally conjugated chains. In the case of 6c, a chemo- and stereoselective…
Selectivity in the direction of photoisomerization reactions in liquid-crystalline guest-host systems
E ⇄ Z photoisomerization reactions of stilbenes la-c were studied in liquid-crystalline (LC) phases and in the corresponding isotropic melts. Whereas viscosity has a moderate influence on the photostationary states, a strong effect caused by the regular incorporation of the stilbene molecules in the LC phases was observed. The direction of the isomerization can be reversed, up to the case of a one-way isomerization Z E for the tailored guest-host system 1b/BS. Such an LC-matrix effect is of typical highly ordered (smectic) phases with free volumina which are strictly limited by hydrophobic interactions; it could not be detected in a much more mobile nematic phase. Textures based on the bire…