Poly(phenylene vinylene)‐based copolymers containing 3,7‐phenothiazylene and 2,6‐pyridylene chromophores: Fluorescence sensors for acids, metal ions, and oxidation

Abstract

A novel copolymer, poly(N‐hexyl‐3,7‐phenothiazylene‐1,2‐ethenylene‐2,6‐pyridylene‐1,2‐ethenylene) (P3), containing N‐hexyl‐3,7‐phenothiazylene and 2,6‐pyridylene chromophores was synthesized to investigate the effect of protonation, metal complexation, and chemical oxidation on its absorption and photoluminescence (PL). Poly(N‐hexyl‐3,8‐iminodibenzyl‐1,2‐ethenylene‐1,3‐phenylene‐1,2‐ethenylene) and poly(N‐hexyl‐3,7‐phenothiazylene‐1,2‐ethenylene‐1,3‐phenylene‐1,2‐ethenylene) (P2), consisting of 1,3‐divinylbenzene alternated with N‐hexyl‐3,8‐iminodibenzyl and N‐hexyl‐3,7‐phenothiazylene, respectively, were also prepared for comparison. Electrochemical investigations revealed that P3 exhibited lower band gaps (2.34 eV) due to alternating donor and acceptor conjugated units (push–pull structure). The absorption and PL spectral variations of P3 were easily manipulated by protonation, metal chelation, and chemical oxidation. P3 displayed significant bathochromic shifts when protonated with trifluoroacetic acid in chloroform. The complexation of P3 with Fe3+ led to a significant absorption change and fluorescence quenching, and this implied the coordination of ferric ions with the 2,6‐pyridylene groups in the backbone. Moreover, both phenothiazylene‐containing P2 and P3 showed conspicuous PL quenching with a slight redshift when oxidized with NOBF4. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1272–1284, 2004

Phenothiazinyl- and 4-diethylaminophenyl-substituted diethylenes as fluorescent and hole-transporting molecular materials

“…1,3-Xylene-bis(triphenylphosph onium bromide), biphenyl-4,4 0 -diyl-dimethyldi(triphenylphosph onium chloride) and 4,4 0 -di[(diethoxyphosphonyl)methyl]biphenyl were synthesized by the known procedures [16,17].…”

Luminescence properties of PPV-based conjugated polymers containing phenothiazine and phenothiazine-5-oxide units

“…Phenothiazine is a well-known heterocyclic compound with electron-rich nitrogen and sulfur heteroatom. Conjugated polymers and copolymers based on phenothiazine have been investigated [1][2][3][4][5][6][7]. It has been demonstrated that phenothiazine unit is an excellent p-type building block for lowering ionic potential of conjugated polymers due to its readily injection and transport of hole and the non-planarity of phenothiazine impedes p-stacking aggregation and intermolecular excimer formation which may lead to the poor quantum efficiency.…”

Electrochemical synthesis, characterization and electrochromic properties of indan and 1,3-benzodioxole-based poly(2,5-dithienylpyrrole) derivatives

“…π-Conjugated polymers such as carbazole, triphenylamine (TPA), and thiophene-based materials have gained much attention during the past decade due to their promising applications in electrochromic devices [1][2][3][4][5], smart windows [6], light-emitting diodes (LEDs) [7][8][9], organic solar cells [10,11], catalyst [12][13][14], sensors [15][16][17], and organic field effect transistors [18]. Among them, recent interest has focused tremendously on the application of conducting polymers (CPs) in electrochromic materials owing to their outstanding coloration efficiency, rapid A C C E P T E D M A N U S C R I P T color-switching ability [19], and broad color availability through fine-tuning bandgap with modification of their chemical structures [20].…”