Crystal structure and self-assembly property of sandwich-type mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes

Abstract

Two sandwich-type mixed (phthalocyaninato)(porphyrinato) rare earth double-decker complexes, M(Pc)(TPP) [H2Pc=phthalocyanine; H2TPP=meso-tetra(phenyl)porphyrin] (M=Eu, Lu) (1, 2) were synthesized and the structure of Lu(Pc)(TPP) was characterized by X-ray single-crystal diffraction method. Crystal data: triclinic, space group P1¯, Z=2, C77H45Cl3LuN12, Mr=1419.57, a=12.573(5), b=12.911(5), c=22.935(5)Å, α=103.793(5)°, β=101.363(5)°, γ=93.682(5)°, V=3521(2)Å3, μ(Mo Kα)=1.196mm−1, F(000)=1426, R=0.0590, and wR=0.1639 for 9745 observed reflections with I>2σ(I). X-ray analysis reveals that the coordination polyhedron adopts a slightly distorted square-antiprismatic structure around the metal center. Both phthalocyanine and porphyrin ligands are saucer-shaped, with the skew angle of the two ligand planes approximately 45°. The self-assembled nano-structures of both complexes 1 and 2 were systematically investigated by electronic absorption and Fourier transform infrared (FT-IR) spectroscopy, transmission electronic microscopy (TEM), scanning electronic microscopy (SEM), and X-ray diffraction (XRD) techniques, revealing the effect of molecular structure on the dimension of self-assembled nano-structures.