Polymeric Layers Catenated by Ribbons of Rings in a Three-Dimensional Self-Assembled Architecture: A Nanoporous Network with Spongelike Behavior

Abstract

The current interest in the crystal engineering of polymeric coordination networks [1] stems from their potential applications as zeolite-like materials [2] for molecular selection, ion exchange, and catalysis, as well as in the intriguing variety of architectures and topologies. Particularly attractive are the novel types of supramolecular intertwinings observed in these species, that still need a rational classification. According to Batten and Robson [3] an ªinterpenetrating frameworkº is comprised of motifs that are infinite and inextricably entangled, that is, they cannot be separated without breaking links. On this basis, we must exclude some interesting polymeric entanglements recently described, including polymeric catenanes, [4] infinite double helices, [5] two-dimensional clothlike warp-and-weft sheets, [6] and other noteworthy supramolecular architectures. [7] For ªtrueº interpenetrating networks, however, different classes can be envisaged. The dominant type (ªclass Aº) is represented by 2D or 3D species that are comprised of a limited number of individual frames of equal topology that interpenetrate into an array with the same original dimensionality as in, for example, n-fold parallel interpenetrating hexagonal layers (n 6) or diamondoid nets (n 9). [3] Other types of interpenetration have been observed in coordination polymers that are reminiscent of molecular catenanes and rotaxanes. Some examples of polymeric catenated species are illustrated in Figure 1. In contrast to the class A interpenetrated nets, these examples all show the following features: 1) the constituent motifs have a lower dimensionality than that of the resulting architectures; 2) each individual motif is intertwined only with the surrounding ones and not with all the others, as ªa ring in a chainº; and 3) the concept of ªn-foldicityº cannot be used in the same sense as for class A. [13] We report here on a new member of this class of catenated motifs, 1, obtained from the selfassembly of copper(ii) sulfate and 1,3-bis(4-pyridyl)propane (bpp).[Cu 5 (bpp) 8 (SO 4 ) 4 (EtOH)(H 2 O) 5 ](SO 4 )´EtOH´25.5 H 2 O 1[3] a) M.

The social behavior of older animals. By Anne Innis Dagg. Baltimore: Johns Hopkins University Press, 2009. Pp. ix +225

“…Die Umwandlung findet statt, wenn ein gastfreier Wirt in die flüssige Phase einer Gastverbindung eingetaucht oder Gastmoleküldampf ausgesetzt wird 45. 126, 132, 153, 156, 162, 167, 203, 285, 287, 288, 290, 295–297, 299, 310, 311, 314, 315, 318, 322–324, 333, 334, 372, 376–379 Bemerkenswerterweise können sogar überkritische Gase (N 2 , O 2 , CH 4 ) die Strukturumwandlung auslösen 152. 161 Diese Strukturumwandlungen sind im Wesentlichen mit den im vorigen Abschnitt eingeführten Funktionssynthons verknüpft (Tabelle 5, Abbildung 36), die auf 1) Koordinationsbindungen, 2) Wasserstoffbrücken und 3) anderen schwachen nichtbindenden Wechselwirkungen (π‐π‐Stapel‐ und Van‐der‐Waals‐Kräften) basieren.…”

Poly[dichloridobis[μ-1-(4-pyridylmethyl)-1H-1,2,4-triazole]copper(II)]

“…For background on the synthesis and structures of coordination polymers, see: Carlucci et al (2000Carlucci et al ( , 2004; Effendy et al (2003); Evans et al (1999); Huang et al (2006); Liu et al (2005); Moulton & Zaworotko (2001); Ranford et al (1999); Sharma & Rogers (1999).…”

“…Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97. In the research of supramolecular chemistry, a great interest has recently been focused on the crystal engineering of coordination frameworks due to their intriguing architectures, new topologies, intertwining phenomena and potential applications in microelectronics, nonlinear optics, ion exchange, molecular selection, molecular separation and recognition (Carlucci et al, 2000;Evans et al, 1999;Ranford et al, 1999;Sharma et al, 1999). The structural motifs of coordination polymers rest on several factors, but the choice of appropriate ligands is no doubt the key factor because it has an obvious influence on the topologies of coordination polymers and behavior of the molecules.…”

Poly[diaqua(μ2-1,3-di-4-pyridylpropane-κ2N:N′)(μ2-thiophene-2,5-dicarboxylato-κ2O:O′)nickel(II)]: a two-dimensional bilayered coordination polymer

“…For related literature, see: Biradha et al (2002); Bourne et al (2001); Carlucci et al (2000Carlucci et al ( , 2002; Chen et al (2006Chen et al ( , 1999Chen et al ( , 1998; Deng et al (2006); Eddaoudi et al (2002); Fu et al (2003); Konar et al (2004); Lou et al (2006); Luan et al (2005); Pan et al (2001); Plater et al (2000); Wang et al (2005); Wu et al (2005); Zhang et al (2006Zhang et al ( , 2003.…”

“…Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b) and Mercury (Macrae et al, 2006); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999 As an important structural unit, linear bipyridyl ligands such as 4,4′-bipyridine (Wang et al, 2005;Chen et al, 2006;Lou et al, 2006) and 4,4′-bipyridyl with rigid or flexible spacers (Plater et al, 2000;Biradha et al, 2002;Fu et al, 2003;Wu et al, 2005) have been extensively employed to construct novel metal-organic coordination polymers with intriguing structural topologies and unexpected properties with potential applications as functional materials. The compound 1,3di-4-pyridylpropane (bpp) is a bipyridine-type ligand with a flexible -CH 2 CH 2 CH 2 -spacer, and a number of metal-bpp coordination polymers have been reported (Carlucci et al, 2000(Carlucci et al, , 2002Pan et al, 2001;Luan et al, 2005). Thiophene-2,5-dicarboxylic acid (H 2 tda), which is similar to other dicarboxylic acids, such as benzene-1,3-dicarboxylic acid (Bourne et al, 2001;Zhang et al, 2003;Konar et al, 2004), shows diverse coordination modes and can act as a mono-, bi-, tri-or tetradentate ligand (Chen et al, 1998(Chen et al, , 1999Eddaoudi et al, 2002;Zhang et al, 2006;Deng et al, 2006).…”