Department of Chemistry, Harran University, 63300 Sanlıurfa, Turkey.
Spectrochim Acta A Mol Biomol Spectrosc. 2012 Dec;98:207-14. doi: 10.1016/j.saa.2012.07.122. Epub 2012 Aug 4.
Several new copper(II) complexes (4-6) with N-dimethoxyphenyl-3,5-(t)Bu(2)-salicylaldimine ligands abbreviated as N-R-3,5-DTBS, where R=2,4-dimethoxyphenyl (1), 2,5-dimethoxyphenyl (2) and 3,5-dimethoxyphenyl (3) have been prepared and their spectroscopic (IR, (1)H NMR, UV/Vis, ESR), magnetic and redox reactivity are described. The ESR spectra of frozen-solution 4-6 and solid state 4 and 5 are indicative of axially symmetric g-tensor (g([parallel])>g([perpendicular])>2.03). The powder ESR spectrum of 6 is unusual for CuN(2)O(2) type systems and exhibits "reversed" type (g([parallel])<g([perpendicular])) signal with a rhombic g-tensor g(3) (2.235)>g(2) (2.128)>g(1) (2.019) pattern indicative of a d(z)(2) ground state. Chemical oxidation of 4 and 6, as supported by ESR and UV/Vis techniques, generates new Cu(II) species and Cu(II)-phenoxyl radicals. The CV studies have shown that the complexes possess ligand-centered and copper(II)-centered quasi-reversible and irreversible responses.
已经制备了几个带有 N-二甲氧基苯基-3,5-(t)Bu(2)-水杨醛亚胺配体的新型铜(II)配合物（4-6），缩写为 N-R-3,5-DTBS，其中 R=2,4-二甲氧基苯基（1）、2,5-二甲氧基苯基（2）和 3,5-二甲氧基苯基（3）。描述了它们的光谱（IR、（1）H NMR、UV/Vis、ESR）、磁性和氧化还原反应性。4-6 的冷冻溶液和 4 和 5 的固态 ESR 光谱表明存在各向同性 g 张量（g([parallel])>g([perpendicular])>2.03）。6 的粉末 ESR 谱对于 CuN(2)O(2) 型系统来说是不寻常的，并且表现出“反向”类型（g([parallel])<g([perpendicular])）信号，具有菱形状 g 张量 g(3) (2.235)>g(2) (2.128)>g(1) (2.019)模式，表明 d(z)(2) 基态。ESR 和 UV/Vis 技术支持的 4 和 6 的化学氧化生成了新的 Cu(II)物种和 Cu(II)-苯氧自由基。CV 研究表明，这些配合物具有配体中心和铜(II)中心准可逆和不可逆响应。
