Institute of Fundamental Sciences, Massey University, Private Bag 11 222, Palmerston North, New Zealand.
Inorg Chem. 2013 Aug 19;52(16):9327-37. doi: 10.1021/ic400829d. Epub 2013 Aug 8.
The synthesis and spectroscopic analysis of both "metal-only" and anion encapsulated salicylaldoxime-based complexes utilizing a new 1,3-xylyl strap are described. X-ray crystallographic analysis reveals that the aromatic spacer restricts the confirmation flexibility of the resulting complexes leading to dicopper(II) double helicate and dicopper(II) 2 + 2 "box" structural forms. The choice of the structural motif is influenced by the anion present, with the copper(II) nitrate-containing complex NO3⊂(Cu2L(3)2)3, 4, adopting a double helicate form, whereas the analogous copper(II) bromide complexes 2Br⊂(Cu2L(3)2)2, 5, and 2Br⊂(Cu2L(3)2)2, 6, both adopt 2 + 2 "box" structural configurations. Spectroscopic analysis has shown an enhancement in the binding strength of ClO4(-) over the anions SO4(2-) and NO3(-). The enhanced rigidity caused by the use of the 1,3-xylyl spacer in this series of complexes has favored the formation of the "double loaded" dibromide complex.
描述了利用新的 1,3-二甲苯基肩带合成和光谱分析“仅含金属”和阴离子包封的水杨醛肟基配合物。X 射线晶体学分析表明，芳香间隔基限制了所得配合物的构象灵活性，导致双铜（II）螺旋和双铜（II）2 + 2“盒”结构形式。结构基序的选择受存在的阴离子影响，含铜（II）硝酸盐的配合物[NO3⊂（Cu2L（3）2）]（NO3）3，4，采用双螺旋形式，而类似的铜（II）溴化物配合物[2Br⊂（Cu2L（3）2）]（Br）2，5 和[2Br⊂（Cu2L（3）2）]（BF4）2，6，均采用 2 + 2“盒”结构构型。光谱分析表明，ClO4（-）对阴离子 SO4（2-）和 NO3（-）的结合强度增强。在该系列配合物中使用 1,3-二甲苯基间隔基导致增强的刚性有利于“双负载”二溴化物配合物的形成。
