Details

Autor(en) / Beteiligte

• Wang, Yan
• Huang, Yong-Qing
• Liu, Guang-Xiang
• Okamura, Taka-aki
• Doi, Mototsugu
• Sheng, Yue-Wei
• Sun, Wei-Yin
• Ueyama, Norikazu

Titel

New Metal-Organic Frameworks with Large Cavities: Selective Sorption and Desorption of Solvent Molecules

Ist Teil von

• Chemistry : a European journal, 2007-01, Vol.13 (26), p.7523-7531

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2007

Quelle

Wiley-Blackwell Journals

Beschreibungen/Notizen

• Five novel transition metal complexes [CdII3(tpba‐2)2(SCN)6]⋅6 THF⋅3 H2O (1), [CuII3(tpba‐2)2(SCN)6]⋅6 THF⋅3 H2O (2), [NiII3(tpba‐2)2(SCN)6]⋅6 THF⋅3 H2O (3), [CdII2(tpba‐2)(SCN)3]ClO4 (4), [CuI3(SCN)6(H3tpba‐2)] (5) [TPBA‐2 = N′,N′′,N′′′‐tris(pyrid‐2‐ylmethyl)‐1,3,5‐benzenetricarboxamide, THF=tetrahydrofuran] were obtained by reactions of the corresponding transition metal salts with TPBA‐2 ligand in the presence of NH4SCN using layering or solvothermal method, respectively. The results of X‐ray crystallographic analysis showed that complexes 1, 2 and 3 are isostructural and have the same 2D honeycomb network structure with Kagomé lattice, in which all the MII (M = Cd, Cu, Ni) atoms are six‐coordinated, and the TPBA‐2 ligands adopt cis,cis,cis conformation while the thiocyanate anions act as terminal ligands. Capsule‐like motifs are found in 1, 2 and 3, in which six THF molecules are hosted, and the results of XPRD and solid‐state 13C NMR spectral measurements showed that the compound 1 can selectively desorb and adsorb THF molecules occurring along with the re‐establishment of its crystallinity. In contrast to 1, 2 and 3, complex 4 has different 2D network structure, resulting from TPBA‐2 ligands with cis,trans,trans conformation, thiocyanate anions serving as end‐to‐end bridging ligands, and the incomplete replacement of perchlorate anions, which further link the 2D layers into 3D framework by the hydrogen bonds. In complex 5, the CuII atoms are reduced to CuI during the process of solvothermal reaction, and the CuI atoms are connected by thiocyanate anions to form a 3D porous framework, in which the protonated TPBA‐2 ligands are hosted in the cavities as templates. Five novel metal–organic frameworks with flexible tripodal ligands containing carboxamide groups were obtained and their structures were determined by single crystal X‐ray diffraction analyses. The selective encapsulations for solvent molecules are reported.