Coordination Polymers with a Bulky Perylene-Based Tetracarboxylate Ligand: Syntheses, Crystal Structures, and Luminescent Properties
Chun-Sen Liu A B , Min Hu A , Song-Tao Ma A , Qiang Zhang A , Li-Ming Zhou A , Li-Jun Gao A and Shao-Ming Fang A BA Zhengzhou University of Light Industry, Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou, Henan 450002, China.
B Corresponding authors. Email: chunsenliu@zzuli.edu.cn; smfang@zzuli.edu.cn
Australian Journal of Chemistry 63(3) 463-473 https://doi.org/10.1071/CH09411
Submitted: 28 July 2009 Accepted: 29 September 2009 Published: 26 March 2010
Abstract
To explore the coordination possibilities of perylene-based ligands with a larger conjugated π-system, four ZnII, MnII, and CoII coordination polymers with perylene-3,4,9,10-tetracarboxylate (ptc) and the chelating 1,10-phenanthroline (phen) ligands were synthesized and characterized: {[Zn2(ptc)(phen)2](H2O)10}∞ (1), {[Zn3(ptc)(OH)2(phen)2](H2O)3}∞ (2), {[Mn(ptc)0.5(phen)(H2O)2](H2O)1.5}∞ (3), and {[Co(ptc)0.5(phen)(H2O)2](H2O)2.5}∞ (4). Structural analysis reveals that complexes 1 and 2 both take one-dimensional polymeric chain structures with dinuclear and trinuclear units as nodes, respectively, which are further extended via the accessorial secondary interchain interactions, such as C–H···O H-bonding or aromatic π···π stacking interactions, to give rise to the relevant higher-dimensional frameworks. Compound 3 has a two-dimensional sheet structure that is further assembled to form a three-dimensional framework by interlayer π···π stacking interactions. Complex 4 is a one-dimensional ribbon-like array structure that is interlinked by the co-effects of intermolecular π···π stacking and C–H···π supramolecular interactions, resulting in a higher-dimensional framework from the different crystallographic directions. Moreover, complexes 1–4 exhibit strong solid-state luminescence emissions at room temperature, which mainly originate from intraligand π→π* transitions of ptc.
Acknowledgements
This work was supported by the National Natural Science Funds of China (grant nos 20801049 and 20771095), the Natural Science Funds of Henan Province (grant no. 0611022700), and the Startup Fund for PhDs of Natural Scientific Research of Zhengzhou University of Light Industry (grant nos 2007BSJJ001 and 2006BSJJ001 to C.-S.L. and S.-M.F., respectively).
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