We report on the novel chiral push-pull chromophores derived from 6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine (Tröger's base skeleton). The synthesis of symmetrical chromophores featuring two identical acceptors, as well as the synthesis of unsymmetrical chromophores featuring only one acceptor is given. Symmetrical chromophores were prepared in the enantiomerically pure form and their chiroptical properties were investigated. Second-order nonlinear optical (NLO) properties of new chromophores were investigated with the aid of hyper-Rayleigh scattering (HRS). The detailed theoretical analysis of the second-order NLO properties of the chromophores was also undertaken. The joint theoretical and experimental studies of chromophores derived from Tröger's base skeleton, in comparison with benchmark chromophores featuring a dimethylamino group as the donor, provided insight into the relationship between the structure of the new chromophores and their NLO properties.
a b s t r a c tNovel, push-pull chromophores combining a cationic benzothiazolium acceptor moiety and either one or two thiophene rings as a part of the conjugated p-system between the donor and the acceptor moieties have been synthesized and characterized. The chromophores displayed pronounced quadratic NLO activity with their first molecular hyper polarizabilities in agreement with their linear spectral properties.
We report on the synthesis and electronic spectra of the chiral, donor-acceptor (push-pull) chromophores (AE)-4 and (AE)-5 with a 6H, 12H-5,11-methanodibenzo[b,f][1,5]diazocine scaffold (Scheme 1 and Fig. 2). The electronic structures of these compounds were investigated at a quantumchemical level (Figs. 2 and 3). The chemical reactivity of 6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine ((AE)-11) towards aromatic electrophilic substitution (Scheme 2 and Table) provided additional information about its electronic structure and confirmed nonnegligible delocalization of the lone pair of the bridge-head N-atoms in this heterocyclic system.
The title compound, C15H6F8N2, possesses a non-crystallographic twofold axis. The dihedral angle between the two benzene rings is 98.4 (2)°. The crystal structure involves intermolecular C—H⋯F hydrogen bonds.
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