Aluminum Complexes of N2O23- Formazanate Ligands Supported by Phosphine Oxide Donors.
Aluminum Complexes of N2O23- Formazanate Ligands Supported by Phosphine Oxide Donors.
复制标题
氧化膦供体支持的 N2O23-甲氨基甲酸配体的铝配合物。
作者：
R. Maar;A. Rabiee Kenaree;Ruizhong Zhang;Y. Tao;Benjamin D. Katzman;V. Staroverov;Z. Ding;J. Gilroy
报道了一类新的膦氧化物固载的甲酸铝配合物（7a，B，8a，9a）的合成与表征。X-射线衍射研究表明，在固态配合物中的铝原子采用八面体几何构型。赤道位置由N2 O23-甲氮杂环丁烷配体占据，轴向位置由L-型氧化膦供体占据。紫外-可见吸收光谱表明，配合物在500 ~ 700 nm之间有很强的吸收（ε = 30000 M-1 cm-1）。用含时密度泛函理论模拟了该区域的最大吸收。除3-氰基取代的配合物7 b在过量氧化膦存在下显示最大发光强度外，标题配合物在溶液和固态下均不发光。用循环伏安法研究了配合物的电化学性质。每个配合物在-0.12至0.29 V和0.62至0.97 V的电位范围内进行连续的单电子氧化，相对于二茂铁/二茂铁氧化还原对。在-1.34和-1.75 V之间的电位下观察到电化学还原事件。与作为共反应物的三正丙胺组合，络合物7 b充当电化学发光发射体，其在735 nm的波长处具有最大电化学发光强度，相对于相同化合物的光致发光最大值红移。
The synthesis and characterization of a new family of phosphine oxide supported aluminum formazanate complexes (7a,b, 8a, 9a) are reported. X-ray diffraction studies showed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an N2O23- formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ≈ 30000 M-1 cm-1) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density functional theory. With the exception of 3-cyano-substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are nonemissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of -0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between -1.34 and -1.75 V. In combination with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound.