Structural changes in non-planar octaaryl substituted phthalocyanine phosphorus complexes
Structural changes in non-planar octaaryl substituted phthalocyanine phosphorus complexes
复制标题
DOI：
10.1142/s1088424615500364
复制
发表时间：
2015-01-01
影响因子：
1.5
通讯作者：
Kobayashi, Nagao
中科院分区：
文献类型：
--
作者：
Furuyama, Taniyuki;Harako, Ryosuke;Kobayashi, Nagao
将磷(V)离子引入游离基酞菁2a和2b中，合成了非平面α -八芳基酞菁衍生物(（α - ar)(8)Pc）、3a和3b的磷配合物。3a和3b通过MS、H-1和P-31 NMR谱进行了表征。由于磷的原子半径小，3a的固态结构为褶皱Pc结构，而相应的自由碱pc2a则为鞍状Pc结构。磷配合物在近红外区表现出较强的吸收带（q波段），而在外围苯基处引入给电子基团对q波段的额外红移是有效的。电化学数据表明，q波段的红移是由于LUMO和HOMO的显著稳定和适度稳定导致HOMO-LUMO间隙减小所致。MO计算表明，磷(V)离子增强了外围芳基部分与Pc大环核之间的电子相互作用。
Phosphorus complexes of non-planar alpha-octaaryl phthalocyanine derivatives ((alpha-Ar)(8)Pc), 3a and 3b have been synthesized by introduction of phosphorus(V) ions into free-base Pcs 2a and 2b. 3a and 3b were characterized by MS, H-1 and P-31 NMR spectra. The solid state structure of 3a indicated a ruffled Pc structure due to the small atomic radius of phosphorus, although the corresponding free-base Pc 2a has a saddled Pc structure. The phosphorus complexes showed intense absorption bands (Q-bands) in the near-IR region, while the introduction of electron-donating groups at the peripheral phenyl groups was efficient for additional red-shifting of the Q-band. Electrochemical data revealed that the red-shift of the Q-band is attributable to a decrease in the HOMO-LUMO gap due to significant and moderate stabilization of the LUMO and HOMO, respectively. MO calculations suggested that the phosphorus(V) ion intensified the electronic interaction between the peripheral aryl moieties and the Pc macrocyclic core.