Synthesis and Optical Properties of 1,4- and 1,2-Dicyanodibenzodioxins Possessing Donor–π-Acceptor Architecture

Abstract

The synthesis and photophysical characterization of isomeric 1,4-and 1,2-dicyanodibenzodioxins is reported. The molecules exhibit optical spectra in the visible region and possess large (ca. 100 nm) Stokes shifts. The synthetic protocol is simple and high-yielding and the presence of replaceable fluorine atoms on the activated dibenzodioxin moiety provides the opportunity for further transformation towards molecules bearing push–pull architecture.

Key words

dibenzodioxins - push–pull molecules - intramolecular charge transfer - long-wavelength absorption - Stokes shift

• References and Notes

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• 22 Synthesis of Compound 14 To a solution of 11 (60 mg, 0.22 mmol) in MeCN (10 mL) was added NaOMe (60 mg, 1.1 mmol) at r.t. The mixture was stirred for 1 h, monitored by TLC (EtOAc–PE) for consumption of starting material. The reaction mixture was quenched with H₂O (30 mL), extracted with CH₂Cl₂ (50 mL), the organic layer washed with brine (10 × 10 mL), dried over Na₂SO₄, filtered, and concentrated using a rotary evaporator. Compound 14 was isolated by column chromatography purification (SiO₂ gel, eluent 10% EtOAc–PE) as a pale green powder; yield: 31 mg (50%). ¹H NMR (300 MHz, CDCl₃): δ = 7.05–7.03 (m, 4 H), 4.12–4.11 (m, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 151.00, 147.60, 144.30, 144.15, 141.20, 139.62, 139.56, 126.00, 117.05, 116.96, 109.84, 109.78, 108.37, 96.53, 96.27, 62.47, 62.38. UV/Vis (DMSO): λ_max (log ε) = 262 (3.63), 390 (3.53) nm. HRMS (ESI⁺): m/z calcd for C₁H₇FN₂O₃Na [M + Na]: 305.0338; found: 305.0328.
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