A Hybrid Consisting of Coordination Polymer and Noncovalent Organic Networks:  A Highly Ordered 2-D Phenol Network Assembled by Edge-to-Face π−π Interactions

Abstract

A 2-D metal-organic open framework having 1-D channels, [Cu(C(10)H(26)N(6))](3)[C(6)H(3)(COO)(3)](2).18H(2)O (1), was constructed by the self-assembly of the Cu(II) complex of hexaazamacrocycle A (A = C(10)H(26)N(6)) with sodium 1,3,5-benzenetricarboxylate (BTC(3)(-)) in DMSO-H(2)O solution. 1 crystallizes in the trigonal space group P with a = b = 17.705(1) A, c = 6.940(1) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 1884.0(3) A(3), Z = 1, and rho(calcd) = 1.428 g cm(-3). The X-ray crystal structure of 1 indicates that each Cu(II) macrocyclic unit binds two BTC(3-) ions in a trans position and each BTC(3-) ion coordinates three Cu(II) macrocyclic complexes to form 2-D coordination polymer layers with honeycomb cavities (effective size 8.1 A), and the layers are packed to generate 1-D channels perpendicularly to the 2-D layers. Solid 1 binds guest molecules such as MeOH, EtOH, and PhOH with different binding constant and capacity. By the treatment of 1 with aqueous solution of phenol, a hybrid solid [Cu(C(10)H(26)N(6))](3)[C(6)H(3)(COO)(3)](2).9PhOH.6H(2)O (2) was assembled. 2 crystallizes in the trigonal R3 space group with a = b = 20.461(1) A, c = 24.159(1) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 8759.2(7) A(3), Z = 3, and rho(calcd) = 1.280 g cm(-3). In 2, highly ordered 2-D noncovalent phenol layers are formed by the edge-to-face pi-pi interactions between the phenol molecules and are alternately packed with the coordination polymer layers in the crystal lattice.

New Porous Lanthanide‐Organic Frameworks: Synthesis, Characterization, and Properties of Lanthanide 2,6‐Naphthalenedicarboxylates

“…( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) as Zn II , [9] Cu II , [14] and Co II [17,18] as d-block metal ions have low coordination numbers and the coordination sites of dblock metal ions are easily occupied by the carboxylates, therefore interpenetration of the framework is less likely to occur. Lanthanide ions have higher coordination numbers, and it is more difficult to predict or control the coordination frameworks of lanthanide ions than their d-block analogues.…”

Isocationic substitution of copper(II) complexes in anisotropic materials based on benzenetricarboxylate

“…Alcohols are the most common adsorbates in these studies [3][4][5][6][7]. This activity may be attributed to the hydrophilic nature of the cavity surfaces in the lattices of these OMF and the possibility of forming hydrogen bonds between the interacting components.…”

“…Crystal hydrates are a particular class of OMF consisting of copper(II) and nickel(II) azamacrocyclic complexes and aromatic carboxylates and form a broad range of lattices with cavities and/or channels or laminar structure [2]. As a consequence of these features, such OMF are capable of adsorbing some organic and inorganic molecules either from the gas phase or liquids [2].Alcohols are the most common adsorbates in these studies [3][4][5][6][7]. This activity may be attributed to the hydrophilic nature of the cavity surfaces in the lattices of these OMF and the possibility of forming hydrogen bonds between the interacting components.…”

“…The similarity of the volume of OMF cavities and the total volume of the adsorbed alcohol molecules such as methanol and ethanol indicates binding of the guests in the adsorbent channels. On the other hand, in the case of phenol, this parameter is not always related to the cavity volume due to the possibility of intercalation of the adsorbate between the adsorbent layers [3,4]. The structural factor, i.e., agreement of the pore size and geometrical parameters of the adsorbate is not a principal requirement in the adsorption of small monohydric alcohols but becomes predominant in interaction with large molecules.…”

Solvothermal synthesis and structural characterization of a novel erbium(III)-carboxylate polymeric complex

“…However, evolution of an assembly, in all these cases, normally depends on the properties of the functional group under consideration. Therefore, the assembly of molecular materials from organic ligands and metal ion building blocks to generate new supramolecular architectures is still a challenge [3][4].…”