Synthesis and Electronic Properties of Monodisperse Oligophenothiazines

Abstract

Starting from N-hexylphenothiazine, a versatile construction kit of brominated and borylated phenothiazines can be easily prepared by a sequence of bromination, bromo-lithium exchange/borylation, and Suzuki coupling. Subsequent Suzuki arylation of the building blocks gives soluble, monodisperse, and structurally well defined oligophenothiazines in good yields. The molecular weights at the peak maximum (Mp), obtained by GPC (gel permeation chromatography), and the actual molecular weights of the oligomer series, obtained by mass spectrometry, show excellent correlation. A QM/MM conformational analysis for the complete series reveals that the obvious butterfly-shaped phenothiazine structure multiplies and significantly reduces the hydrodynamic volume of the oligomers. The electronic properties (absorption and emission spectroscopy and cyclic voltammetry) give reasonable correlations with the chain length. With regard to the emission maxima, the effective conjugation length is already reached with the hexamer. Oligophenothiazines are highly fluorescent, with high fluorescence quantum yields, and are simultaneously highly electroactive, with low oxidation potentials.

Chemical Synthetic Platform for Chlorpromazine Oligomers That Were Reported as Photo-degradation Products of Chlorpromazine

“…and bromide 3 22) followed by removal of the Boc groups under acidic conditions and subsequent reductive methylation of the generated secondary amines then successfully afforded CPZ dimer 1 (n=2). To demonstrate practicality of our synthetic platform, the synthetic protocol was applied to preparation of CPZ trimer 1 (n=3) (Chart 5).…”

Synthesis and structure of new 3,7,10-substituted-phenothiazine derivatives

“…The yields varied in this case from fair to good. In order to elaborate procedures for the synthesis of other intermediates we transformed compound 6 into its diboronic ester 14 (by a procedure taken from the literature [19]) and then by a palladium catalyzed Suzuki coupling reaction [20][21][22][23][24][25] of macrocycles, which after similar modifications with those shown for 2-4 could be transformed into the mercapto derivatives and then deposited on gold 1.1.1 surface.…”

Synthesis, Photovoltaic Properties and Side-chain Effect of Copolymer Containing Phenothiazine and 2,1,3-Benzothiadiazole

“…The collected organic layer dried with MgSO4 and the solvent was removed through vacuum evaporation. Then, purified by using column chromatography to obtain the product [22,25,26] 2.4.4. 10-(Alkyl)-3,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaboraolan-2-yl)-10H-phenothiazine (M1a-c) In a 2-neck flask, 6 mmol of 3,7-dibromo-10-(alkyl)-10H-phenothiazine is completely dissolved in 50 mL THF and stirred at -78 ℃ under nitrogen.…”

“…The mixture was poured into water, extracted with ether, and dried with MgSO4. The crude product was purified by recrystallization with ethanol [22,26,27 2.4.6. 1,2-Dinitro-4,5-bis(octyloxy)benzene In 1000 mL 3-neck flask, 62.77 mmol of 1,2-dioctlyoxybenzene and 90 mL of acetic acid was dissolved 90 mL of MC and stirred at 0 ℃ for 1 h under nitrogen atmosphere.…”