Well-Structured Narrow Near-Infrared Absorption Based on Nonaggregated Hexarylene-Bisimide toward a Colorless Dye | The Journal of Organic Chemistry pubs.acs.org/doi/10.1021/... #PiSky
Well-Structured Narrow Near-Infrared Absorption Based on Nonaggregated Hexarylene-Bisimide toward a Colorless Dye
Extended π-conjugated systems are often insoluble, and their aggregation manner greatly affects their absorption spectra. This study produced a planar, soluble, and nonaggregated hexarylene-bisimide (HB) with appropriate substituents. The single-crystal X-ray structure of HB confirmed the planar molecular structure with small twist angles and the dimerization behavior of HB in the solid state. The concentration-dependent 1H NMR experiments in CDCl3 indicated that the association constant Kdimer is 4.6 × 103 M–1 at 298 K and ΔGdimer (298 K) = −20.8 kJ mol–1. The longest absorption of HB at the monomeric state exhibits a sharp and intense peak at 921 nm (ε = 230,000 M–1 cm–1, full width at half-maximum = 718 cm–1) in toluene. 75% of the absorption of HB above 400 nm appears in the near-infrared region, thus giving a practically colorless solution. Magnetic circular dichroism spectra of a series of oligorylene-bisimides reveal the predominant contribution of the linear polyene-like conjugation over the annulene-like conjugation for larger [n]oligorylene-bisimides.
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