Synthesis, Structure, Spectroscopic Studies, and Complexation of Novel Crown Ether Butadienyl Dyes

Abstract

Dedicated to Professor Andre¬ M. Braun on the occasion of his 60th birthday Butadienyl dyes of the benzothiazole series with various fragments of benzocrown ethers 1a ± c were synthesized for the first time. The structures and spectral properties of crown-containing butadienyl dyes and their complexes with alkali and alkaline-earth metal cations were studied by X-ray diffraction analysis and 1 H-NMR, UV/VIS, and resonance Raman spectroscopy. To interpret the experimental results, quantumchemical calculations were performed. In the case of Sr 2 and Ba 2 ions, the formation of strong sandwich complexes [M(1b) 2 ] 2 of an unusual structure involving stacking interactions was established; the dye molecules are arranged one above another in the complex according to the −head-to-head× pattern.

Effect of Interchromophoric Stacking Interactions on the Stability of the Sandwich-Type Complexes of 1-Hydroxy-9,10-anthraquinone-9-iminobenzo-15-crown-5 ether with Metal Cations

“…В Таблице 1 представлены значения lgK 1:1 и lgK 2:1 , а также спектральные характеристики комплексов лиганда 2 и B15C5 с катионами металлов I и II групп. Константы K 1:1 для B15C5⋅Mg 2+ и B15C5⋅Ca 2+ были измерены нами ранее, [17] а данные для комплексов B15C5 с катионами щелочных металлов взяты из работы.…”

Crown Ether Based Optical Molecular Sensors and Photocontrolled Ionophores

“…[5][6][7][8][9][10][11] Compounds 3 and 4 are representatives of the crown-containing styryl dyes that show negative ionochromism. [6,7] The N-methylazacrown fragment in 4 proved to be better preorganized for binding of metal ions than the N-phenylazacrown fragment in 3.…”

“…The complex stability constants for 6 with the diammonium dications are significantly higher than those with the corresponding monocations (the lgK values for It is known that the replacement of one or several oxygen atoms in crown ethers by sulphur atoms dramatically changes the ion-binding selectivity. For example, the chromogenic dithia-18-crown-6 ether 7 [10] derived from a butadienyl dye exhibits a very low affinity for alkali and alkaline earth cations in comparison with its 18-crown-6 ether analogue, [11] but it forms very stable complexes with Hg 2+ and Ag + both in organic solvents and in water.…”

Crown-containing butadienyl dyes 8. Structures and complexation of chromogenic dithia-15(18)-crown-5(6) ethers

“…Crown con taining styryl and butadienyl dyes are examples of chromo ionophores, which show cation induced hypsochromic shifts. [7][8][9] The properties of chromogenic crown ethers as selec tive reagents for the colorimetric determination of alkali and alkaline earth cations are rather well studied, whereas the possibilities of the use of macrocyclic ligands for the design of optical molecular chemosensors for transition and heavy metal cations were not fully explored.…”

“…3 Ethyl 2 [(1E,3E) 4(2,3,5,6,8,9,11,12 octahydro 1,7,13,4,10 benzotrioxadithiacyclopentadecyn 15 yl) 1,3 butadienyl] 1,3 benzothiazolium perchlorate (2a) and 3 ethyl 2 [ ( 1 E , 3 E ) 4 ( 2 , 3 , 5 , 6 , 8 , 9 , 1 1 , 1 2 , 1 4 , 1 5 d e c a h y d r o 1,7,10,16,4,13 benzotetraoxadithiacyclooctadecyn 18 yl) 1,3 butadienyl] 1,3 benzothiazolium perchlorate (2b) were prepared by condensation of the corresponding dithiacrown containing cinnamaldehydes 21 with 3 ethyl 2 methylbenzothiazolium per chlorate in ethanol. The synthesis will be described in de tail elsewhere.…”