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• 18716-76-2 [Dy(acetylacetonate)₃]·nH₂O 
• 22112-77-2 5,10,15,20-tetra-(4-chlorophenyl)porphyrin 

Relevant academic research and scientific papers

Sandwich-type mixed tetrapyrrole rare-earth triple-decker compounds. Effect of the coordination geometry on the single-molecule-magnet nature

Employment of the raise-by-one step method starting from M(TClPP)(acac) (acac = monoanion of acetylacetone) and [Pc(OPh)8]M′[Pc(OPh) 8] led to the isolation and free modulation of the two rare-earth ions in the series of four mixed tetrapyrrole dysprosium sandwich complexes {(TClPP)M[Pc(OPh)8]M′[Pc(OPh)8]} [1-4; TClPP = dianion of meso-tetrakis(4-chlorophenyl)porphyrin; Pc(OPh)8 = dianion of 2,3,9,10,16,17,23,24-octa(phenoxyl)phthalocyanine; M-M′ = Dy-Dy, Y-Dy, Dy-Y, and Y-Y]. Single-crystal X-ray diffraction analysis reveals different octacoordination geometries for the two metal ions in terms of the twist angle (defined as the rotation angle of one coordination square away from the eclipsed conformation with the other) between the two neighboring tetrapyrrole rings for the three dysprosium-containing isostructural triple-decker compounds, with the metal ion locating between an inner phthalocyanine ligand and an outer porphyrin ligand with a twist angle of 9.64-9.90 and the one between two phthalocyanine ligands of 25.12-25.30. Systematic and comparative studies over the magnetic properties reveal magnetic-field-induced single-molecule magnet (SMM), SMM, and non-SMM nature for 1-3, respectively, indicating the dominant effect of the coordination geometry of the spin carrier, instead of the f-f interaction, on the magnetic properties. The present result will be helpful for the future design and synthesis of tetrapyrrole lanthanide SMMs with sandwich molecular structures.

Mixed (porphyrinato)(phthalocyaninato) rare-earth(III) double-decker complexes for broadband light harvesting organic solar cells

Solution-processed organic-inorganic hybrid bulk heterojunction solar cells with the capability of broadband solar photon harvesting over the ultraviolet-visible-near-infrared spectral range are developed. A series of mixed (porphyrinato)(phthalocyaninato) rare-earth double-decker complexes, [MIIIH(TClPP){Pc(α-OC4H9)8}] (1-7; M = Y, Sm, Eu, Tb, Dy, Ho, Lu; TClPP = meso-tetrakis(4-chlorophenyl) porphyrinate; Pc(α-OC4H9)8 = 1,4,8,11,15,18,22,25-octakis(1-butyloxy)phthalocyaninate) and [Y III(TClPP)(Pc)] (8, Pc = unsubstituted phthalocyaninate), along with a heteroleptic bis(phthalocyaninato) yttrium double-decker complex [Y IIIH(Pc){Pc(α-OC4H9)8}] (9), are synthesized and utilized as broadband absorbers and electron donors (D), whereas N,N′-bis(1-ethylhexyl)-3,4:9,10-perylenebis(dicarbox-imide) (PDI) or [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) is adopted as primary electron acceptor (A1). For suppressing the fatal back charge transfer at D/A1 interface, the D:A1 blend is fabricated within an in situ formed cheap inorganic network of nanoporous TiOx, which can act as a secondary electron acceptor (A2). For characterization of these structures, steady state spectroscopy, fluorescence dynamics, atomic force microscopy, current-voltage characteristics, and photoelectrical properties of the active materials or devices are investigated. Solar cells utilizing PDI as the primary acceptor show higher values in open circuit voltage, fill factor, and power conversion efficiency over those cells using PCBM as the primary acceptor. With a cell area of 0.36 cm2, good efficiencies of up to 0.82% are achieved by the aforementioned double-decker complex:PDI:TiOx blends under 1-sun air mass 1.5 global illumination. These results conclude that double-decker bis(tetrapyrrole) complexes are promising photovoltaic materials with tunable absorption and photophysical properties.