Reversible Phase Transformation and Luminescence of Cadmium(II)-Dipyridylamide-Based Coordination Frameworks

• Published in: Chemistry : a European journal Vol. 18; no. 51; pp. 16443 - 16449
• Main Authors: Tzeng, Biing-Chiau, Wei, Sheng-Luen, Chang, Tsung-Yi
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 14.12.2012; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Assembly; cadmium; Chemistry; coordination frameworks; Diffraction; Economic growth; Ethers; Heating; Luminescence; phase transitions; rotaxanes; Studies; Transformations; Two dimensional; X-rays
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201202916

We have synthesized a series of 1D double‐zigzag ({[Cd(paps)2(H2O)2](ClO4)2}n (1), {[Cd(papo)2(H2O)2](ClO4)2}n (3), and {[Cd(papc)2(H2O)2](ClO4)2}n (5)) and 2D polyrotaxane frameworks ([Cd(papc)2(ClO4)2]n (6)) by the reaction of Cd(ClO4)2 with dipyridylamide ligands N,N′‐bis(pyridylcarbonyl)‐4,4′‐diaminodiphenyl thioether (paps), N,N′‐bis(pyridylcarbonyl)‐4,4′‐diaminodiphenyl ether (papo), and N,N′‐(methylenedi‐p‐phenylene)bispyridine‐4‐carboxamide (papc), respectively, where their molecular structures have been determined by X‐ray diffraction studies. Based on the powder X‐ray data (PXRD) of compound 3 and its ZnII analogue, heating the double‐zigzag framework of compound 3 can give the polyrotaxane framework of [Cd(papo)2(ClO4)2]n (4) and grinding this powder sample in the presence of moisture resulted in its complete conversion back into the pure double‐zigzag framework. In addition, heating the double‐zigzag frameworks of compounds 1 and 5 can induce structural transformation into their respective polyrotaxanes, whereas grinding these solid samples in the presence of moisture did not lead to the formation of the double zigzags. Herein, we investigated the effect of the metal (from ZnII to CdII) on the assembly process and luminescence properties, as well as on the particularly intriguing structural transformation of a series of papx‐based frameworks. In fact, the assembly behavior and luminescence properties of the CdIIpapx and ZnIIpapx frameworks were really similar. However, both ZnIIpapx (x=s, o) frameworks can perform reversible structural transformation, but only the CdIIpapo framework can do it. Therefore, a delicate metal effect on such a new structural transformation can be observed. Zig and zag: The effect of a metal on the interconversion between 1D double‐zigzag and 2D polyrotaxane frameworks of CdII–papo by heating and grinding was investigated by X‐ray diffraction (see figure; papo=N,N′‐bis(pyridylcarbonyl)‐4,4′‐diaminodiphenyl ether).