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Reversible Phase Transformation and Luminescence of Cadmium(II)–Dipyridylamide‐Based Coordination Frameworks
Author(s) -
Tzeng BiingChiau,
Wei ShengLuen,
Chang TsungYi
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202916
Subject(s) - luminescence , zigzag , crystallography , thioether , powder diffraction , chemistry , ether , phase (matter) , materials science , stereochemistry , organic chemistry , geometry , mathematics , optoelectronics
Abstract We have synthesized a series of 1D double‐zigzag ({[Cd(paps) 2 (H 2 O) 2 ](ClO 4 ) 2 } n ( 1 ), {[Cd(papo) 2 (H 2 O) 2 ](ClO 4 ) 2 } n ( 3 ), and {[Cd(papc) 2 (H 2 O) 2 ](ClO 4 ) 2 } n ( 5 )) and 2D polyrotaxane frameworks ([Cd(papc) 2 (ClO 4 ) 2 ] n ( 6 )) by the reaction of Cd(ClO 4 ) 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 Zn II analogue, heating the double‐zigzag framework of compound 3 can give the polyrotaxane framework of [Cd(papo) 2 (ClO 4 ) 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 Zn II to Cd II ) 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 Cd II papx and Zn II papx frameworks were really similar. However, both Zn II papx (x=s, o) frameworks can perform reversible structural transformation, but only the Cd II papo framework can do it. Therefore, a delicate metal effect on such a new structural transformation can be observed.