金属铂(Ⅱ)-卟啉二聚体配合物的分子内π-π相互作用（英文）

Intramolecular π-π Interactions in Platinum(Ⅱ) Metalloporphyrin Dimer Homologues with Aliphatic Chains of Different Lengths

合成了以不同链长的烷氧基柔性链相连接的金属铂(Ⅱ)-卟啉二聚体配合物并对其热稳定性,光谱性质及电化学性质做了研究。在浓度由10-7mol·dm-3增大到10-3mol·dm-3的过程中将配体与配合物的紫外-可见吸收光谱与光致发光光谱做了对比,发现配体与配合物的吸收光谱随浓度变化未出现改变,但发射光谱显现出随浓度增大而产生红移现象。当烷氧基柔性链中碳原子数大于4时,C6与C10配合物无论是高浓度下的溶液与升华固体薄膜中的荧光发射光谱均比配体有明显的红移,而短链的配合物无此性质。

The synthesis and thermal stabilities, spectroscopic and electrochemical properties for a series of platinum（n） metalloporphyrin dimer complexes with aliphatic chain of different lengths [-O（CH2）nO-] have been studied. Although dimeric porphyrin ligands and platinum（n） complexes display nearly the same absorption spectra in the concentration range from 10-7 to 10-4 mol-dm-3, these ligands and their complexes show concentration- dependent emission when the length of aliphatic chain is beyond four carbon atoms. At elevated concentration of the ligands and complexes, the emission spectra show obvious red-shifts. For complex Pt2C6（OPTPP）2 and Pt2C10 （OPTPP）2, the emission maxima at 652 nm are red-shifted to 676 and 681 nm at concentrations 〉10-4 mol .dm-3. Emission spectra of the sublimate films of complexes also display similar red-shifts： 43 nm for Pt2C6（OPTPP）2 and 53 nm for Pt2C10（OPTPP）2. The concentration-dependent emission indicates that there are intramolecular π-π interactions in porphyrin dimers and platinum（H） metalloporphyrins.