Molecular Cage, One‐Dimensional Tube and Two‐Dimensional Polycatenane obtained from Reactions of Flexible Tripodal Ligand 1,3,5‐Tris(imidazol‐1‐ylmethyl)‐2,4,6‐trimethylbenzene with Copper Salts

Abstract

Three novel copper complexes, [Cu II (titmb)(N 3 ) 2 ]·0.5H 2 O (1), [Cu I 3 (titmb) 2 ](ClO 4 ) 3 (2), and [Cu II (titmb)(SO 4 )]·2.2H 2 O (3), were obtained by reactions of flexible tripodal ligand 1,3,5-tris-(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) with the corresponding copper(II) salts using hydrothermal method and their structures were determined by X-ray crystallography. Complex 1 exhibits a one-dimensional (1D) tube-like chain structure, while the 2 possesses a M 3 L 2 molecular cage-like structure, in which the copper atom has a valence of ϩ1, indicating that the Cu II is reduced to Cu I under the hydrothermal condition. Complex 3 has a polycatenated network structure with inclined interpenetration of (6,3) networks. Ligand titmb adopts a cis,cis,cis-conformation in all of the three complexes. The results indicate that the anions play important roles in the structure of the complexes. In addition, complex 2 was further investigated by electrospray massspectrometry.

Isostructural Synthesis of Porous Metal–Organic Nanotubes

“…A material’s molecular dimensionality plays a critical role in defining its unique properties. − For example, the dimensionalities of different allotropes of carbon (diamond, graphene, and carbon nanotubes) result in very different applications, differences that are manifested even between graphene and carbon nanotubes, both of which have the same hybridization at each carbon atom (Figure ). − Metal–organic frameworks (MOFs) are a significant class of porous materials, and similar to carbon, MOFs can be designed as 3D, 2D, and 1D materials. − While 2D and 3D MOFs have been well-developed and have found numerous applications in gas and liquid separations, − catalysis, − and chemical sensing (Figure ), ,, their 1D counterparts, metal–organic nanotubes (MONTs), are still in their infancy . A limited number of MONTs have been synthesized, − and while a majority of reports have focused solely on structural details, MONTs have already shown promise in highly selective adsorptions. ,,, An interest in these tubular nanomaterials whose potential remains largely unexplored has compelled coordination chemists to develop rational methodologies that allow for their preparation and study.…”

Synthesis and Characterization of Copper(II)–Phosphonate Coordination Chain Array of Metallocages

“…It is noteworthy that the formation of M 4 L 2 ‐metallocage structure by tripodal‐like ligand (H 2 tpmm 4− ) here is rarely observed, since that a M 4 L 2 ‐metallocage structure is usually built by tetrapodal ligands, while a tripodal ligand in general forms a M 3 L 2 ‐metallocage structure . Moreover, this case is comparable with the Cu(II)−tris‐phosphonate complex [Cu 4 (H 2 tpmm) 2 (H 2 O) 4 ], which has an M 4 L 2 ‐metallocage unit similar to the metallocages MC‐A and MC‐B in compound 1 .…”

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

“…[14] The coordination environment around the Cu I was shown in Figure 6a. It can be clearly seen that the TPBA-2 ligand did not participate in the coordination with the metal atoms and all the Cu I atoms are four-coordinated with two N atoms from two thiocyanate anions and two S atoms from another two thiocyanate anions, in which the CuÀN bond lengths are 1.960(4) and 1.970 (4) , and the CuÀS bond lengths are 2.2991(12) to 2.4440 (14) (Table S1, Supporting Information), respectively. The N-Cu-S, N-Cu-N and S-Cu-S coordination angles vary from 100.94(5) to 116.48 (13) coordination geometry with a N 2 S 2 donor set.…”