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DOI: 10.1055/a-2086-0530
Synthesis of Heavy-Atom-Free Triplet Photosensitizers Based on Organoboron Complexes
This work is supported by Department of Atomic Energy, Govt. of India.
Abstract
A new class of organoboron complexes have been developed as heavy-atom-free triplet photosensitizers. A methodology was developed for the synthesis of an indolocarbazole–imine boron difluoride (IIBD) dye and its dimer from a 6-formylindolocarbazole. The IIBD dye was then coupled with a BODIPY dye through the C-2 or C-8 position of the latter to synthesize two dyads. Both dyads showed superior photophysical properties to those of the IIBD dyes. The relative triplet conversion efficiencies of these dyes were determined by measuring their singlet-oxygen (1O2) generation capacities. All the synthesized dyes showed high 1O2 generation compared with the BODIPY dye PM567. The dyad linked through the C-2 position of the BODIPY core showed the highest 1O2 generation efficiency, which could be useful for photodynamic therapy of cancers.
Key words
indolocarbazoles - dye - organoboron compounds - BODIPY dyes - triplet photosensitizers - photocatalystsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2086-0530.
- Supporting Information
Publication History
Received: 15 March 2023
Accepted after revision: 04 May 2023
Accepted Manuscript online:
04 May 2023
Article published online:
05 June 2023
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- 26 Schiff Bases 2, 4, 8, and 13; General ProcedureThe appropriate aryl amine, a catalytic amount of PTS, and anhyd Na2SO4 (100 mg) were added to a solution of 12-pentyl-5,11-dihydroindolo[3,2-b]carbazole-6-carbaldehyde (1) in anhyd DCE (20 mL), and the mixture was stirred at 70 °C for 12 h. The mixture was then filtered and concentrated under vacuum, and the residue was subjected to column chromatography (basic alumina, EtOAc–hexane).Compound 4Prepared by following the general procedure from p-phenylenediamine (28 mg, 0.25 mmol) and 1 (200 mg, 0.56 mmol) in DCE (20 mL) and purified by column chromatography [basic alumina, hexane–EtOAc (70:30)] to give a red solid; yield: 142 mg (32%); mp >300 °C.1H NMR (500 MHz, DMSO-d 6, 25 °C, TMS): δ = 0.89 (t, J = 7.0 Hz, 3 H), 1.38–1.42 (m, 2 H), 1.58–1.60 (m, 2 H), 1.88–1.90 (m, 2 H), 3.16 (t, J = 8.0 Hz, 2 H), 7.24–7.30 (m, 2 H), 7.47–7.48 (m, 2 H), 7.64 (d, J = 8.0 Hz, 1 H), 7.87 (s, 2 H), 7.91 (d, J = 8.0 Hz, 1 H), 8.22 (d, J = 8.0 Hz, 1 H), 8.47 (d, J = 8.0 Hz, 1 H), 10.06 (s, 1 H), 11.43 (s, 1 H), 11.86 (s, 1 H). 13C{1H} NMR (125 MHz, DMSO-d 6, 25 °C, TMS): δ = 14.1, 22.3, 28.6, 28.8, 31.6, 109.8, 111.4, 111.9, 114.6, 118.8, 119.1, 120.3, 120.5, 121.8, 121.9, 122.1, 122.7, 123.1, 123.7, 125.3, 125.8, 134.3, 134.6, 140.6, 140.9, 141.6, 147.8, 152.0. EI-MS: m/z = 780.4 [M+].BF2 Complexes 3, 5, 9, and 14; General ProcedureA mixture of the appropriate Schiff base and Et3N in anhyd DCE was stirred at 25 °C for 15 min. BF3·OEt2 was then added dropwise and the resulting mixture was stirred at 70 °C overnight. The reaction was quenched with sat. aq NaHCO3, and the mixture was extracted with CH2Cl2. The organic layer was washed with H2O (3 × 50 mL) and dried (Na2SO4). After removal of the solvent under a vacuum, the residue was purified by column chromatography (silica gel).Compound 5Prepared by the reaction of 4 (121 mg, 0.16 mmol), Et3N (0.3 mL, 1.86 mmol), and BF3·OEt2 (0.2 mL, 1.86 mmol) in DCE (10 mL) according to the general procedure. The crude product was purified by column chromatography [silica gel, EtOAc–PE (30:70)] to give a dark-blue solid; yield: 100 mg (73%); mp >300 °C.1H NMR (500 MHz, DMSO-d 6, 80 °C, TMS): δ = 0.93 (t, J = 7.0 Hz, 6 H), 1.45–1.46 (m, 4 H), 1.64–1.65 (m, 4 H), 1.97–1.98 (m, 4 H), 3.73 (t, J = 8.0 Hz, 4 H), 7.28 (s, 2 H), 7.42 (s, 2 H), 7.55 (s, 4 H), 7.71 (d, J = 7.5 Hz, 2 H), 7.88 (d, J = 7.5 Hz, 2 H), 8.08 (s, 4 H), 8.28 (d, J = 7.5 Hz, 2 H), 8.55 (d, J = 8.0 Hz, 2 H), 9.79 (s, 2 H), 11.61 (s, 2 H). 13C{1H} NMR (125 MHz, DMSO-d 6, 80 °C, TMS): δ = 13.3, 21.7, 28.4, 28.8, 31.1, 106.7, 111.7, 113.6, 116.2, 119.1, 119.6, 120.9, 121.9, 122.9, 123.8, 125.3, 125.7, 126.3, 133.9, 135.7, 139.9, 141.0, 143.1, 143.3, 158.0. EI-MS: m/z = 876.3 [M+].