Rational Design of Supramolecular Gridlike Layers and Zigzag Chains through a Unique Interplay of d10-d10 and -
详细信息 查看全文
- 作者：Augustin M. Madalan ; Narcis Avarvari ; and Marius Andruh
- 刊名：Crystal Growth & Design
- 出版年：2006
- 出版时间：July 2006
- 年：2006
- 卷：6
- 期：7
- 页码：1671 - 1675
- 全文大小：371K
- 年卷期：v.6,no.7(July 2006)
- ISSN：1528-7505
文摘
Six new Cu(II)-M(I) complexes (M = Ag, Au) were synthesized to illustrate the role of the convolution of d10-d10(aurophilic or argentophilic) and 
- stacking interactions in sustaining supramolecular solid-state architectures. Two types ofsupramolecular synthons are involved: a rectangular one, based on the aurophilic (argentophilic) interactions between the [M(CN)2]-spacers, and a linear one, relying upon - contacts between the aromatic ligands. The reactions between [Cu(acac)(BB)(H2O)](ClO4) complexes and K[M(CN)2] in a 2:1 molar ratio (BB = 2,2'-bipyridine; 1,10-phenanthroline) lead to the following heterotrinuclearcomplexes: [{Cu(acac)(bipy)}2{Au(CN)2}](ClO4)·0.5CH3CN (1), [{Cu(acac)(bipy)}2{Ag(CN)2}](ClO4)·0.5CH3CN (2), [{Cu(acac)(phen)}2{Ag(CN)2}](ClO4) (3), and [{Cu(acac)(phen)}2{Au(CN)2}](ClO4) (4). The recrystallization of 4 from acetonitrile affords[{Cu(acac)(phen)}2{Au(CN)2}](ClO4)·0.5CH3CN (5), which is isomorphous with the compounds 1-3. By reacting [Cu(sal)(bipy)]ClO4 with K[Ag(CN)2] in a 1:1 molar ratio, a heterobinuclear complex, [{Cu(sal)(bipy)}{Ag(CN)2}] (6), is obtained (sal- is theanion of the salicylaldehyde). The copper(II) ions in compounds 1-6 exhibit a square-pyramidal geometry, with the apical positionoccupied by the nitrogen atom from the cyano bridge. As expected, the crystallographic investigation of compounds 1-3 and 5reveals the formation of supramolecular grids resulting from the combination of the two supramolecular synthons. The M···Mdistances in these compounds are 1: 3.295(11) (Au···Au); 2: 3.2144(7) (Ag···Ag), 3: 3.2789(10) (Ag···Ag); 5: 3.389(7) (Au···Au) Å, while the distances associated with the - stackings vary between 3.3 and 3.6 Å. The crystal structure of 4 differs fromthat found in the other trinuclear complexes. It consists of supramolecular chains resulting from the aromatic interaction betweenthe organic ligands attached to the copper ions, without the intervention of the d10-d10 interactions. The analysis of the packingdiagram for compound 6 reveals supramolecular zigzag chains, resulting from the convolution of Ag···Ag [2.9708(5) Å] and -aromatic (3.27-3.55 Å) interactions.
- stacking interactions in sustaining supramolecular solid-state architectures. Two types ofsupramolecular synthons are involved: a rectangular one, based on the aurophilic (argentophilic) interactions between the [M(CN)2]-spacers, and a linear one, relying upon - contacts between the aromatic ligands. The reactions between [Cu(acac)(BB)(H2O)](ClO4) complexes and K[M(CN)2] in a 2:1 molar ratio (BB = 2,2'-bipyridine; 1,10-phenanthroline) lead to the following heterotrinuclearcomplexes: [{Cu(acac)(bipy)}2{Au(CN)2}](ClO4)·0.5CH3CN (1), [{Cu(acac)(bipy)}2{Ag(CN)2}](ClO4)·0.5CH3CN (2), [{Cu(acac)(phen)}2{Ag(CN)2}](ClO4) (3), and [{Cu(acac)(phen)}2{Au(CN)2}](ClO4) (4). The recrystallization of 4 from acetonitrile affords[{Cu(acac)(phen)}2{Au(CN)2}](ClO4)·0.5CH3CN (5), which is isomorphous with the compounds 1-3. By reacting [Cu(sal)(bipy)]ClO4 with K[Ag(CN)2] in a 1:1 molar ratio, a heterobinuclear complex, [{Cu(sal)(bipy)}{Ag(CN)2}] (6), is obtained (sal- is theanion of the salicylaldehyde). The copper(II) ions in compounds 1-6 exhibit a square-pyramidal geometry, with the apical positionoccupied by the nitrogen atom from the cyano bridge. As expected, the crystallographic investigation of compounds 1-3 and 5reveals the formation of supramolecular grids resulting from the combination of the two supramolecular synthons. The M···Mdistances in these compounds are 1: 3.295(11) (Au···Au); 2: 3.2144(7) (Ag···Ag), 3: 3.2789(10) (Ag···Ag); 5: 3.389(7) (Au···Au) Å, while the distances associated with the - stackings vary between 3.3 and 3.6 Å. The crystal structure of 4 differs fromthat found in the other trinuclear complexes. It consists of supramolecular chains resulting from the aromatic interaction betweenthe organic ligands attached to the copper ions, without the intervention of the d10-d10 interactions. The analysis of the packingdiagram for compound 6 reveals supramolecular zigzag chains, resulting from the convolution of Ag···Ag [2.9708(5) Å] and -aromatic (3.27-3.55 Å) interactions.