Supramolecular patterns of cationic and neutral Ni(II) complexes from the interplay of hydrogen-bonding, stacking interactions and metal-coordination motifs
Supramolecular patterns of cationic and neutral Ni(II) complexes from the interplay of hydrogen-bonding, stacking interactions and metal-coordination motifs
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DOI：
10.1039/c2ce25704a
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发表时间：
2012-09
期刊：
影响因子：
3.1
通讯作者：
Konstantina A. Kounavi;E. Moushi;M. Manos;Constantina Papatriantafyllopoulou;A. Tasiopoulos;V. Nastopoulos
中科院分区：
文献类型：
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作者：
Konstantina A. Kounavi;E. Moushi;M. Manos;Constantina Papatriantafyllopoulou;A. Tasiopoulos;V. Nastopoulos
为了探索过渡金属配合物晶体结构的化学亚基在固态中通过非共价相互作用以周期性有序排列在一起的方式，对一系列13个镍（II）配合物进行了研究。从一般的NiII/X−/L或HL ' [X−= Cl−,Br−,I−,NO3−,NO2−，ClO4−]中分离得到配合物；L = 1-甲基-4,5-二苯基咪唑和HL ' = 4,5-二苯基咪唑]反应体系。单晶衍射分析表明，与所使用的配体无关，大多数配合物含有刚性的方形平面[NiL4]2+(1-5)或[Ni(HL ')4]2+(6-10)阳离子，这似乎通过采用结构导向作用对自组装过程产生影响：超分子组装通过与周围的反离子/溶剂团簇在每个单独的结构中相互作用而组织在刚性的大块阳离子周围。簇的组分OH−/H2O(1)、[NiCl4]2 - /EtOH(2)、Br−/H2O(3)、NO3−/MeOH(4)、ClO4−/Me2CO(5)、Cl−/H2O(6)、Br−/MeCN(7)、I−/Me2CO/H2O(8)、NO3−/EtOH/H2O(9)和ClO4−/Me2CO（10）通过强弱氢键紧密结合在一起。阳离子的结构导向作用是通过弱C-H⋯O/Cl/Br−，π⋯π和C-H⋯π相互作用（对于含l的配合物）或强循环的N-H⋯/Cl−/Br−/I−/O基序以及弱相互作用（对于含HL ' -配合物）主导分子自组装来完成的。在所研究的化合物中观察到的立体化学的多样性（正方形平面，1-10；四面体，11和12；八面体，13）似乎主张选择镍作为金属超分子研究的有趣候选者。
In an effort to explore the way in which the chemical subunits of crystal structures of transition metal complexes are put together in periodic ordered arrays in the solid state via noncovalent interactions, an investigation on a series of 13 nickel(II) complexes has been carried out. The complexes were isolated from the general NiII/X−/L or HL′ [X− = Cl−, Br−, I−, NO3−, NO2−, ClO4−; L = 1-methyl-4,5-diphenylimidazole, and HL′ = 4,5-diphenylimidazole] reaction system. A single-crystal diffraction analysis shows that, independently of the ligand used, most of the complexes contain the rigid square planar [NiL4]2+ (1–5) or [Ni(HL′)4]2+ (6–10) cation, which seems to have an impact on the self-assembly process by adopting a structure-directing role: the supramolecular assembly is organized around the rigid bulky cations via interactions with the surrounding counterion/solvent clusters in each individual structure. The components of the clusters, i.e. OH−/H2O (1), [NiCl4]2–/EtOH (2), Br−/H2O (3), NO3−/MeOH (4), ClO4−/Me2CO (5), Cl−/H2O (6), Br−/MeCN (7), I−/Me2CO/H2O (8), NO3−/EtOH/H2O (9), and ClO4−/Me2CO (10), are held tightly together by strong or weak hydrogen bonding. The structure-directing action of the cations is accomplished via weak C–H⋯O/Cl/Br−, π⋯π and C–H⋯π interactions (for L-containing complexes) or strong recurring N–H⋯/Cl−/Br−/I−/O motifs dominating the molecular self-assembly together with weak interactions (for HL′-containing complexes). The variety of the stereochemistries observed among the studied compounds (square planar, 1–10; tetrahedral, 11 and 12; octahedral, 13) seems to advocate the choice of nickel as an interesting candidate in metallosupramolecular research.