Iglesias Rodrigo S, Claessens Christian G, Torres Tomas, Herranz M Angeles, Ferro Victor R, de la Vega Jose M García
Departamento de Química Orgánica, Universidad Autónoma de Madrid, 28049-Madrid, Spain.
J Org Chem. 2007 Apr 13;72(8):2967-77. doi: 10.1021/jo062608h. Epub 2007 Mar 15.
Subphthalocyanine (SubPc)-fused dimers and trimers bearing fluorine, iodine, and thioether peripheral substituents were synthesized and characterized. Absorption spectroscopy and electrochemical studies revealed (i) that the substituents have a strong effect on the electronic properties of the macrocycles and (ii) that there is good communication between the subphthalocyaninic moieties within the oligomeric structures. Theoretical calculations at DFT/6-31G(d,p) computational level and electron density studies support the experimental findings. The frontier orbitals in the dimers and trimers were also shown to be significantly altered with respect to those of SubPcs as a consequence of the extension of the conjugation associated with symmetry breaking. Time-dependent density functional theory calculations reproduced the differences observed in the UV-vis spectra of the fused dimers and the monomeric SubPcs.
合成并表征了带有氟、碘和硫醚外围取代基的亚酞菁（SubPc）稠合二聚体和三聚体。吸收光谱和电化学研究表明：（i）取代基对大环的电子性质有强烈影响；（ii）在低聚结构中亚酞菁部分之间存在良好的相互作用。在DFT/6-31G(d,p)计算水平上的理论计算和电子密度研究支持了实验结果。由于与对称性破缺相关的共轭扩展，二聚体和三聚体中的前沿轨道相对于亚酞菁的前沿轨道也发生了显著变化。含时密度泛函理论计算重现了稠合二聚体和单体亚酞菁紫外-可见光谱中观察到的差异。
