0000000000049416
AUTHOR
Annette Oehlhof
Star-Shaped Compounds Having 1,3,5-Triazine Cores
The 1,3,5-triazine derivatives 1−4 having styryl or higher oligo(phenylenevinylene) chains in the 2-, 4-, and 6-positions represent star-shaped push-pull compounds. Alkoxy or dimethylamino groups on the peripheral benzene rings, which act as electron donors, and the central 1,3,5-triazine ring, which acts as an electron acceptor, cause intramolecular charge transfer (ICT) to occur in the absorption S0⇄S1. Protonation of the 1,3,5-triazine core enhances the effect, as demonstrated by a bathochromic shift; a secondary protonation on the dimethylamino groups, however, leads to the breakdown of the ICT. Thus, the yellow compound 1d first becomes violet and then colorless upon the addition of tr…
Equilibrium between Hydroxycycloalkanones and Oxabicycloalkanols
Guido Kramer, Annette Oehlhof, and Herbert Meier Institute of Organic Chemistry, University of Mainz, Duesbergweg 10 – 14, 55099 Mainz, Germany Reprint requests to Prof. Dr. H. Meier. Fax: +49-(0)6131-3925396. E-mail: hmeier@mail.uni-mainz.de Z. Naturforsch. 2009, 64b, 847 – 850; received April 8, 2009 Hydroxycycloalkanones 1 of medium ring size (8 – 10) exist in a transannular tautomeric equilibrium with the corresponding oxabicycloalkan-1-ols 2, which represent hemiacetals. Normally, the bicyclic structures 2 predominate in solution although their portion decreases with increasing solvent polarity. A correlation of the Gibbs reaction enthalpies ∆G (1→2) with the solvent parameters ET (30)…
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.
Push-Pull Oligomers with 2,2-Dicyanovinyl Groups as Electron Acceptors
Three conjugated oligomer series with terminal donor–acceptor substitution were studied: oligo(1,4-phenylenevinylene)s DAOPVs 4a–d (n = 1–4), oligo(1,4-phenyleneethynylene)s DAOPEs 6a–d (n = 1–4) and oligo(2,5-thienyleneethynylene)s DAOTEs 8a–e (n = 1–5). Dialkylamino or methoxy groups served as electron donors and 2,2-dicyanovinyl groups as strong electron acceptors. The push-pull effect polarizes the molecular chains – an effect which is documented by the splitting of the 13C chemical shifts of two carbon atoms of the double or triple bonds in the chain. For higher oligomers (n ≥ 3), the effect is mainly localized at the chain ends. The long-wavelength absorption results in a charge-trans…
Supramolecular order of stilbenoid dendrons: importance of weak interactions
Stilbenoid dendrons with various donor and acceptor groups on the focal unit were synthesised by a Wittig–Horner reaction, starting from an aldehyde functionalised dendron and various substituted phosphonic acid esters. The target molecules are composed of meta-branched arms, two of them with extended conjugation (distyrylbenzene) and three flexible dodecyloxy chains; the focal group consists of a donor or acceptor substituted styryl unit. The cross-conjugation of the arms prevents the strong electronic influence of substituents on the two extended oligophenylenevinylene chromophores. However, intermolecular interactions mediated by the focal unit allow control of the supramolecular stackin…
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…
Oligo(2,5-thienyleneethynylene)s with Terminal Donor-Acceptor Substitution
Five oligo(2,5-thienyleneethynylene) series (OTE, n = 1–5), namely the push-pull substituted compounds 1b-5b and 1c-5c, the purely donor substituted compounds 1a-5a and two precursor series with protected and deprotected ethynyl end-groups, respectively, were obtained by a convergent synthetic strategy. The extension of the conjugated chromophores in the donor-acceptor OTE (DAOTE) series is superimposed by an intramolecular charge transfer (ICT), which decreases with an increasing number, n, of repeat units. The overall effect is studied by the convergence of the UV/Vis absorption maxima λmax (n) → λ∞ for n → ∞.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)