Dual Emission of meso‐Phenyleneethynylene–BODIPY Oligomers: Synthesis, Photophysics, and Theoretical Optoelectronic Study

Two series of 2,5‐di(butoxy)phenyleneethynylenes, one halogenated (nPEC4‐X; n=2, 3, or 4) and the other boron‐dipyrromethene (BODIPY) terminated (nPEC4‐By; n=3, 4, or 5; By=BODIPY), were synthesized monodirectionally by the step‐by‐step approach and the molecular structure was corroborated by NMR spectroscopy (1H, 13C‐DEPTQ‐135, COSY, HSQC, HMBC, 11B, 19F) and MALDI‐TOF mass spectrometry. The multiplicity and J‐coupling constants of 1H, 11B, and 19F/11B NMR signals revealed, in the nPEC4‐By series, that the phenyl in the meso position of BODIPY becomes electronically part of the conjugation of the phenyleneethynylene chain, whereas BODIPY is electronically isolated. The photophysical, electrochemical, and theoretical studies confirm this finding because the properties of nPEC4‐By are comparable to those of the nPEC4‐X oligomers and BODIPY, indicating negligible electron communication between BODIPY and the nPEC4 moieties. Nevertheless, energy transfer (ET) from nPEC4 to BODIPY was rationalized by spectroscopy and theoretical calculations. Its yield decreases with the nPEC4 conjugation length, according to the increase in distance between the two chromophores, resulting in dual emission for the longest oligomer in which ET is quenched. Double DIPY: meso‐Phenyl‐derived boron‐dipyrromethene (BODIPY), coupled to phenyleneethynylene (PE) oligomers, is electronically isolated from the π‐PE conjugation because of its orthogonality, but displays high energy transfer (ET) efficiencies or dual emission.