Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa.
Department of Chemistry, UiT-The Arctic University of Norway, N-9037 Tromsø, Norway.
Molecules. 2020 Jun 1;25(11):2575. doi: 10.3390/molecules25112575.
A series of novel ferrocenylsubphthalocyanine dyads Y-BSubPc(H) with ferrocenyl-carboxylic acids Y-H = (FcCHCO-H), (Fc(CH)CO-H) or (FcCO(CH)CO-H) in the axial position were synthesized from the parent Cl-BSubPc(H) via an activated triflate-SubPc intermediate. UV/Vis data revealed that the axial ferrocenyl-containing ligand did not influence the Q-band maxima compared to Cl-BSubPc(H). A combined electrochemical and density functional theory (DFT) study showed that Fe group of the ferrocenyl-containing axial ligand is involved in the first reversible oxidation process, followed by a second oxidation localized on the macrocycle of the subphthalocyanine. Both observed reductions were ring-based. It was found that the novel Fc(CH)COBSubPc(H) exhibited the lowest first macrocycle-based reduction potential (-1.871 V vs. Fc/Fc) reported for SubPcs till date. The oxidation and reduction values of Fc(CH)COBSubPc(H) ( = 0-3), FcCO(CH)COBSubPc(H), and Cl-BSubPc(H) illustrated the electronic influence of the carboxyl group, the different alkyl chains and the ferrocenyl group in the axial ligand on the ring-based oxidation and reduction values of the SubPcs.
一系列新型二茂铁基取代酞菁二聚体 Y-BSubPc(H) 用轴向位置的二茂铁羧酸 Y-H = (FcCHCO-H), (Fc(CH)CO-H) 或 (FcCO(CH)CO-H) 合成。通过激活的三氟甲磺酸酯-SubPc 中间体从母体 Cl-BSubPc(H) 得到。UV/Vis 数据表明，与 Cl-BSubPc(H) 相比，轴向含二茂铁的配体不影响 Q 带最大值。电化学和密度泛函理论 (DFT) 研究表明，含二茂铁的轴向配体的 Fe 基团参与了第一个可逆氧化过程，随后是定位于次酞菁大环上的第二个氧化过程。两个观察到的还原都是基于环的。发现新型 Fc(CH)COBSubPc(H) 显示出迄今为止报道的 SubPcs 中最低的第一个大环基于还原电势 (-1.871 V vs. Fc/Fc)。Fc(CH)COBSubPc(H) ( = 0-3)、FcCO(CH)COBSubPc(H) 和 Cl-BSubPc(H) 的氧化和还原值说明了羧基、不同的烷基链和轴向配体中二茂铁基对 SubPcs 的环基氧化和还原值的电子影响。
