A Direct Arylation Approach for the Preparation of Benzothiadiazole-Based Fluorophores for Application in Luminescent Solar ­Concentrators

Dedicated to Prof. Masahiro Murakami on the occasion of his retirement from Kyoto University

Abstract

A straightforward synthetic protocol featuring direct C–H arylations as key steps has been optimized to prepare two benzo-2,1,3-thiadiazole (BTD)-based organic fluorophores. Their light absorption and emission properties, as well as their affinity with poly(methyl methacrylate) as the chosen polymer matrix, were found to be suitable for application in luminescent solar concentrators. Solar-concentration devices were fabricated with both emitters, and their relevant optical and photovoltaic properties are presented.

Key words

direct arylation - fluorophores - benzothiadiazoles - luminescent solar concentrator - photovoltaics

Publication History

Received: 25 January 2023

Accepted after revision: 21 March 2023

Accepted Manuscript online:
21 March 2023

Article published online:
17 April 2023

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• 31 4,7-Bis[7-(9,9-dibutyl-9H-fluoren-2-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl]-2,1,3-benzothiadiazole (LSCA1); Typical Procedure In a Schlenk tube under N₂, compound 3a (122 mg, 0.3 mmol, 1.0 equiv) was dissolved in anhyd toluene together with 2-bromo-9-dibutylfluorene (4; 230 mg, 0.64 mmol, 2.2 equiv), Pd(OAc)₂ (3 mg, 0.015 mmol, 0.05 equiv), CataCXium A (11 mg, 0.03 mmol, 0.1 equiv), PivOH (1 mg, 0.1 mmol, 0.3 equiv), and Cs₂CO₃ (156 mg, 0.45 mmol, 1.5 equiv). The mixture was heated at 95 °C for 18 h, then cooled to r.t., filtered through Celite, and washed with EtOAc (30 mL). The organic phase was washed with H₂O (2 × 10 mL) and brine (10 mL), then dried (Na₂SO₄) and concentrated. The crude solid was purified by flash column chromatography [silica gel, PE–DCM (3:1)] to give a violet solid; yield: 262 mg (0.27 mmol, 90%). ¹H NMR (400 MHz, CD₂Cl₂): δ = 8.52 (s, 2 H), 7.90 (dd, J = 7.9, 1.2 Hz, 2 H), 7.83 (s, 2 H), 7.76–7.71 (m, 4 H), 7.40–7.29 (m, 6 H), 4.47–4.42 (m, 8 H), 2.05 (dt, J = 11.3, 5.0 Hz, 8 H), 1.15–1.06 (m, 8 H), 0.71–0.57 (m, 20 H). ¹³C NMR (100 MHz, CD₂Cl₂): δ = 152.9, 151.7, 151.4, 141.8, 141.3, 140.5, 138.8, 132.5, 127.5, 127.3, 127.0, 125.7, 123.8, 123.4, 120.9, 120.5, 120.2, 120.1, 112.0, 65.5, 65.1, 55.6, 40.7, 26.6, 23.6, 14.2. HRMS (ESI): m/z [M^∙+] calcd for C₆₀H₆₀N₂O₄S₃: 968.3710; found: 968.3715.