标题：Morphology Controlled Nanostructures Self-Assembled from Phthalocyanine Derivatives Bearing Alkylthio Moieties: Effect of Sulfur-Sulfur and Metal-Ligand Coordination on Intermolecular Stacking
作者：Hao, Zijuan; Wu, Xingcui; Sun, Ranran; Ma, Changqin; Zhang, Xiaomei
作者机构：[Hao, Zijuan; Wu, Xingcui; Sun, Ranran; Ma, Changqin; Zhang, Xiaomei] Shandong Univ, Dept Chem & Chem Engn, Jinan 250100, Peoples R China.
通讯作者地址：[Zhang, XM]Shandong Univ, Dept Chem & Chem Engn, Jinan 250100, Peoples R China.
关键词：aggregation; nanostructures; noncovalent interactions; phthalocyanines;; self-assembly
摘要：To investigate the effect of sulfursulfur and metalligand coordination on the molecular structure and morphology of self-assembled nanostructures, metal-free 2,3,9,10,16,17,23,24-octakis(isopropylthio)phthalocyanine H2Pc(beta-SC3H7)8 (1) and its copper and lead congeners CuPc(beta-SC3H7)8 (2) and PbPc(beta-SC3H7)8 (3) are synthesized and fabricated into organic nanostructures by a phase-transfer method. The self-assembly properties are investigated by electronic absorption and Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Experimental results reveal different molecular packing modes in these aggregates, which in turn result in self-assembled nanostructures with different morphologies ranging from nanobelts for 1 through nanoribbons for 2 to cluster nanoflowers for 3. Intermolecular pp and sulfursulfur interactions between metal-free phthalocyanine 1 lead to the formation of nanobelts. The additional Cu?S coordination bond between the central copper ion of 2 and the sulfur atom of the adjacent molecule of 2 in cooperation with the intermolecular pp stacking interaction increases the intermolecular interaction, and results in the formation of long nanoribbons for 2. In contrast to compounds 1 and 2, the special molecular structure of complex 3, together with the intermolecular pp stacking interaction and additional Pb?S coordination bond, induces the formation of Pb-connected pseudo-double-deckers during the self-assembly process, which in turn further self-assemble into cluster nanoflowers. In addition, good semiconducting properties of the nanostructures fabricated from phthalocyanine derivatives 13 were also revealed by IV measurements.