Self-assembly of porphyrin arrays via coordination to transition metal bisphosphine complexes and the unique spectral properties of the product metallacyclic ensembles
Self-assembly of porphyrin arrays via coordination to transition metal bisphosphine complexes and the unique spectral properties of the product metallacyclic ensembles
复制标题
DOI：
10.1021/ja9839825
复制
发表时间：
1999-03-31
影响因子：
15
通讯作者：
Fleischer, EB
中科院分区：
文献类型：
--
作者：
Fan, J;Whiteford, JA;Fleischer, EB
预先设计的有角和线性二吡啶基卟啉模块与双膦配位的 Pd(II) 和 Pt(II) 有角和线性模块的自组装产生包含两个或四个单元且尺寸范围为 15 至 39 埃的环状卟啉阵列。多核核磁共振谱表明这些大环化合物具有高度对称性。反式 DPyDPP 基团围绕由末端金属氮键限定的轴旋转的限制扭曲了四聚体的对称性，但旋转在高温下不受限制。含有 R(+)- 或 S(-)-BINAP 膦的手性金属三氟甲磺酸盐促进对映体大环化合物的形成，手性大环化合物的 CD 光谱揭示了四聚体中卟啉发色团之间的强激子耦合。发射光谱显示，用金属三氟甲磺酸盐处理并同时掺入大环后，二吡啶基卟啉荧光团会发生适度的荧光猝灭。
Self-assembly of predesigned angular and linear dipyridylporphyrin modules with bisphosphine-coordinated Pd(II) and Pt(II) angular and linear modules leads to cyclic porphyrin arrays containing two or four units and ranging in size from 15 to 39 Angstrom. Multinuclear NMR spectra indicate high symmetry for these macrocycles. Restriction in rotation of trans-DPyDPP groups around the axis defined by the terminal metal-nitrogen bonds distorts the symmetry of the tetramers, but the rotation is unrestricted at elevated temperatures. Chiral metal triflates containing R(+)- or S(-)-BINAP phosphines promote formation of enantiomeric macrocycles with a puckered geometry CD spectra of the chiral macrocycles reveal a strong exciton coupling between the porphyrin chromophores in the tetramers. Emission spectra reveal moderate fluorescence quenching of the dipyridylporphyrin fluorophores upon treatment with metal triflates and concomitant incorporation into the macrocycles.