Mixed Phthalocyanine-Porphyrin Fused Conjugated Pentameric Nanoarrays
Yuehong Zhang1, Zheng Xue2, Dongdong Qi1
1Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing, 100083, P. R. China.
Abstract:
The largest phthalocyanine-porphyrin-fused pentameric molecular arrays have been synthesized and spectroscopically characterized. The saddled molecular conformation revealed for the pentamer by DFT-D3 calculation in combination with the bulky peripheral substituents precludes effective face-to-face π-π intermolecular interaction. As a consequence, intermolecular C-H⋅⋅⋅π interactions together with the ubiquitous dispersion force arrays help to self-assemble the representative metal-free pentameric molecules into the three-dimensional supramolecular structures with nanorod morphology in CHCl3 and n-butanol. Powder X-ray diffraction (XRD) analysis and selected area electron diffraction (SAED) disclose the gradually increased long range of molecular ordering in the nanorods along with the increase in the substrate temperature from 30, 40, 50, to 60 °C. This in turn results in an increase in the semiconductivity of the single nanorod in the same order from 9.4×10-9 to 3.8×10-8 , 7.6×10-7 , and 6.3×10-5 S m-1 .
