Ligands H2L in which (10-R-anthracen-9-yl)methyl
moieties (R = H, Me, Et) are covalently joined (6-position) to the
5,7-dioxocyclam macrocycle framework have been prepared and their nickel(II)
complexes isolated and characterized. X-Ray crystal structures of
NiIIL (R = H, Me) complexes show that in both
structures the anthracene moieties are folded around towards the mean plane of
the macrocycles; dihedral angles between the mean anthracene and macrocyclic
planes of c. 22˚ are subtended.
1H n.m.r. spectrometry indicates that the folded
conformations are retained in solution. Absorption and fluorescence spectra,
fluorescence quantum yields and lifetimes of the anthracenyl macrocycles are
reported. Absorption spectra of the metal complexes are red-shifted and the
fluorescence is dramatically quenched compared to the metal-free compounds
indicating a strong electronic interaction between the anthracene and the
complexed dioxocyclam macrocycle.
配体 H2L,其中 (10-R-anthracen-9-yl)methyl
甲基(R = H、Me、Et)共价连接(6 位)到
制备了
配体 H2L,并分离和表征了其
镍 (II)
配合物的分离和表征。以下化合物的 X 射线晶体结构
NiIIL (R = H, Me) 复合物的 X 射线晶体结构显示,在这两种结构中
结构中,
蒽分子都向大环的平均平面折叠。
在这两种结构中,
蒽分子都向大环的平均平面折叠。
平面之间的二面角约为 22˚。
1H n.m.r.光谱分析表明,折叠的
构象保留在溶液中。吸收光谱和荧光光谱、
报告了
蒽基大环的吸收和荧光光谱、荧光量子产率和寿命。
报告。
金属络合物的吸收光谱发生了红移,荧光被显著淬灭。
与不含
金属的化合物相比,荧光被大幅淬灭
这表明
蒽与络合的二氧杂环大环之间存在着强烈的电子相互作用。
络合的二氧杂环大环之间有很强的电子相互作用。