Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC) reactivity was successfully employed to synthesize three donor-acceptor energy transfer (EnT) arrays that contain one (Dyad), three (Tetrad) and four (Pentad) 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) donors connected to a Zn-tetraphenylporphyrin acceptor via 1,2,3-triazole linkages. The photophysical properties of the three arrays, along with individual donor and acceptor chromophores, were investigated by UV-vis absorption and emission spectroscopy, fluorescence lifetimes, and density functional theory (DFT) electronic structure modeling. Comparison of the UV-vis absorption spectra and frontier molecular orbitals from DFT calculations of the three arrays with ZnTPP, ZnTTrzlP, and Trzl-BODIPY shows that the electronic structure of the chromophores is essentially unperturbed by the 1,2,3-triazole linkage. Time-dependent DFT (TDDFT) calculations on the Dyad reproduce the absorption spectra in THF and show no evidence of excited state mixing of the donor and acceptor. The BODIPY singlet excited state emission is significantly quenched in all three arrays, consistent with EnT to the porphyrin core, with efficiencies of 95.8, 97.5, and 97.2% for the Dyad, Tetrad, and Pentad, respectively. Fluorescence excitation spectra of the three arrays, measured at the porphyrin emission, mirror the absorption profile of both the porphyrin and BODIPY chromophores and are consistent with the Förster resonance energy transfer (FRET) mechanism. Applying Förster theory to the spectroscopic data of the chromophores gives EnT efficiency estimates that are in close agreement with experimental values, suggesting that the through-space mechanism plays a dominant role in the three arrays.

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A new azido functionalized 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) has been synthesized to achieve spectral complementarity to a Zn(II) tetraphenylethynyl porphyrin (ZnTPEP). Mixed multilayer films were assembled on glass and quartz up to 10 bilayers thick in a layer-by-layer (LbL) fabrication process using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) to couple these two dyes together with a tris-azido linker. By varying the amount of BODIPY in the CuAAC reaction solutions for the azido linker layers, we achieve tunable doping of BODIPY within the porphyrin films. We are able to demonstrate linear film growth and determine thickness by X-ray reflectivity (XRR). XRR data indicated that lower BODIPY loading leads to higher porphyrin content and slightly thicker films. Fluorescence emission and excitation spectra of the mixed multilayer films show efficient quenching of the BODIPY singlet and enhanced ZnTPEP emission, suggesting efficient energy transfer (EnT). The ease of fabrication and tunability of these films may serve as potential light harvesting arrays for molecular-based solar cells.

Synthesis of Nb2O5 thin films from sputter deposited Nb films and its optical property.