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Photoisomerization of dicyanorhodanine-functionalized thiophenes.

ABSTRACT: π-Conjugated oligomers functionalized with the popular dicyanorhodanine (RCN) electron acceptor are shown to be susceptible to photo-induced Z/E isomerization. The stereochemistry of two model RCN-functionalized thiophenes is confirmed by single crystal X-ray analysis and 2D NMR, and shown to be the thermodynamically stable Z form. Relative energies, Z/E configurations, and conformational preferences are modelled using density functional theory (DFT). The photophysical properties of the model compounds are explored experimentally and computationally; the Z and E isomers display similar absorption profiles with significant spectral overlap and are inseparable upon irradiation to a photostationary state. The well-behaved photoisomerization process is routinely observable by thin-layer chromatography, UV-vis, and NMR, and the photochemical behavior of the two RCN-functionalized thiophenes is characterized under varying wavelengths of irradiation. Ultraviolet (254 nm) irradiation results in photostationary state compositions of 56/44 and 69/31 Z-isomer/E-isomer for substrates functionalized with one thiophene and two thiophenes, respectively. Ambient laboratory lighting results in excess of 10 percent E-isomer for each species in solution, an important consideration for processing such materials, particularly for organic photovoltaic applications. In addition, a photoswitching experiment is conducted to demonstrate the reversible nature of the photoreaction, where little evidence of fatigue is observed over numerous switching cycles. Overall, this work showcases an approach to characterize the stereochemistry and photochemical behavior of dicyanorhodanine-functionalized thiophenes, widely used components of functional molecules and materials.

SUBMITTER: Kornman CT

PROVIDER: S-EPMC8162279 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Two mononuclear and one binuclear ytterbium complexes with dual near-infrared (NIR) photoluminescence and reversible trans-to-cis photoisomerization functions were synthesized and characterized. The central ytterbium(III) ion coordinates with two β-diketonate (4,4,4-trifluoro-1-phenylbutane-1,3-dionate (tfd)) ligands and one deprotonated azobenzene-containing tetradentate ligand [(E)-4-(phenyldiazenyl)-N,N-bis(pyridin-2-ylmethyl) benzohydrazide (HL), (E)-4-((4-(dimethylamino)phenyl)diazenyl)-N,N-bis(pyridin-2-ylmethyl)benzohydrazide (HNL), or (E)-4,4'-N',N'-bis(pyridin-2-ylmethyl)benzohydrazide azobenzene (H2DL)] to form a neutral ternary complex ([Yb(tfd)2L], [Yb(tfd)2(NL)], or [Yb2(tfd)4(DL)], respectively), where the ytterbium(III) ion is eight-coordinated to N3O5 donor sets. X-ray crystallographic analysis shows that all three complexes form a trigonal dodecahedron geometry with similar -N=N- distances that are slightly longer than those of the pure azobenzene-containing ligands. The NIR luminescence properties of the Yb(III) complexes were determined at a wavelength of about 980 nm with quantum yields in the range of 0.4-0.6% in ethanol and acetonitrile solutions at room temperature, and trans-to-cis photoisomerization was determined with the quantum yields (Φt→c = 10-2) at the same level as their pure ligands. The trans-to-cis photoisomerization rates of the complexes (10-4 s-1) are slightly higher than those of the pure ligands and similar to azobenzene (10-5 to 10-4 s-1). From time-dependent density functional theory calculations of the energy levels of the first excited triplet states of the ligands, the energies of the lowest excited triplet states of all of the ligands are higher than the resonance level of Yb3+ (2F5/2, 1.2722 eV). We suggest that these azo-containing ligands may participate in energy transfer to the ytterbium ion, in addition to the main "antenna effect" ligand tfd. This is the first report of azobenzene group-functionalized ytterbium complexes with dual NIR luminescence and photoisomerization properties, indicating that azobenzene-containing lanthanide(III) complexes have potential applications as dual function materials in biological systems.

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Photoisomerization of dicyanorhodanine-functionalized thiophenes.

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