A series of complexes constructed by different calix[4]arene derivatives

Abstract

Thirteen new compounds based on different calix[4]arene derivatives, namely, [Mn(H₃L¹)₂(phen)₃] (1), [Cd(H₃L¹)₂(phen)₃] (2), [Ni(H₃L¹)₂(phen)₃] (3), [Co(H_3.33L¹)₃(phen)₃] (4), [Co(H₃L¹)₂(en)₃]·2H₂O (5), [Zn₂(H₃L¹)₄(en)₄(imi-4)]·H₂O (6), [Zn₆Na₆(L²)₄(OH)₂(imi-4)(H₂O)₄]·5H₂O (7), [Zn₆Na₆(L²)₄(OH)₂(tria-4)(H₂O)₄]·5H₂O (8), [Co₄Na₂(L²)₂(OH)₂(H₂O)₆]·7H₂O (9), [Cu₃Na₂(L²)₂] (10), [Cu₇Na₄(L³)₄(OH)₂(H₂O)₅]·6H₂O (11), [Zn₂Na(L³)(OH)(H₂O)]·2H₂O (12) and [Pb₄Na₂(L³)₂(OH)₂] (13), where H₄L¹ = calix[4]arene, H₄L² = tetra(carboxymethoxy)calix[4]arene, H₄L³ = tetra(carboxymethoxy)(p-tert-butyl)calix[4]arene, phen = 1,10-phenathroline, en = ethylenediamine, imi-4 = 1,4-bis(1H-imidazol-1-yl)butane and tria-4 = 1,4-bis(1,2,4-triazole-1-yl)butane, have been synthesized under hydrothermal conditions. Compounds 1 and 2 are isomorphous. In compound 1, the [Mn(phen)₃]²⁺ unit acts as a guest and was trapped in the dimeric capsule of two H₃L¹ anions. The edge-to-face C–H⋯π interactions between the dimeric capsule hold the [Mn(phen)₃]²⁺ unit and H₃L¹ anion together. Further, face-to-face π–π interactions link the capsules into a three-dimensional (3D) supramolecular architecture. Compounds 3, 4 and 6 show 0D discrete structures, which are further linked by C–H⋯π interactions to form 3D supramolecular architectures, respectively. In compound 5, the [Co(en)₃]²⁺ cations and H₃L¹ anions are linked together through intermolecular hydrogen-bonding interactions, resulting in a 3D supramolecular architecture. Compound 8 is isomorphous with 7. In compound 7, Zn(II) and Na(I) ions are held together by L² anions and imi-4 ligands to generate a 2D layer structure. Compounds 9 and 10 show chain structures, and the chains are linked through hydrogen bonds and C–H⋯π interactions to generate 3D supramolecular architectures, respectively. Compound 11 displays a column structure. Adjacent columns are linked by the C–H⋯O and O–H⋯O interactions to give a 2D supramolecular layer. Compound 12 exhibits a 1D ribbon-like structure. Compound 13 possesses a dimeric structure. The dimers are extended by the C–H⋯O interactions into a 1D supramolecular chain. The powder X-ray diffraction and luminescent properties have also been studied for the compounds.