This study delineates the synthesis and comprehensive characterization of metal complexes of meso-tetrakis(pentafluorophenyl)porphyrin (H₂TPF${}_{20}$P, 1) with first-row transition metal ions (M = Mn(III) 2, Fe(III) 3, Co(II) 4, Ni(II) 5, Cu(II) 6, and Zn(II) 7) to elucidate their structural, electronic spectral, and electrochemical redox properties. Co, Ni, Cu and Zn Complexes exhibit planar structure ($\mathrm{\Delta }$24 = 0.003-0.021 Å and $\mathrm{\Delta }$C${}_{\beta }$ = 0.004−0.041 Å) which is also confirmed by the single crystal data of complex ZnTPF${}_{20}$P, 7 shows the planar geometry, while Fe and Mn complexes show the slightly nonplanar structure ($\mathrm{\Delta }$24 = 0.101–0.143 Å and $\mathrm{\Delta }$C${}_{\beta }$ = 0.080–0.112 Å), which are distorted due to their occupied axial sites by −Cl ligand as revealed by density functional theory (DFT) calculations. Furthermore, electronic spectroscopy revealed a gradual bathochromic shift following the order of NiTPF${}_{20}$P < CoTPF${}_{20}$P < CuTPF${}_{20}$PCl < H₂TPF${}_{20}$P = FeTPF${}_{20}$PCl < ZnTPF${}_{20}$P < MnTPF${}_{20}$PCl by appending different metal ions in the porphyrin core. MnTPF${}_{20}$PCl exhibited the most significant bathochromic shift ($\mathrm{\Delta }{\lambda }_{\text{max}}$ = 63 nm) in the Soret band compared to H₂TPF${}_{20}$P. Also, MnTPF${}_{20}$PCl and FeTPF${}_{20}$PCl show a unique pattern of split Soret band at around 364 and 345 nm due to the interaction between the metal $d$-orbitals and the surrounding ligands. The electrochemical redox potentials of the filled 3d orbital of Zn endow ZnTPF${}_{20}$P (ring centered) with the lowest oxidation potential.

本研究描述了内消旋四（五氟苯基）卟啉（H ₂ TPF ）金属配合物的合成和综合表征${}_{20}$P, 1 ) 与第一行过渡金属离子 (M = Mn(III) 2、Fe(III) 3、Co(II) 4、Ni(II) 5、Cu(II) 6和 Zn(II) 7）阐明其结构、电子光谱和电化学氧化还原特性。Co、Ni、Cu 和 Zn 配合物呈现平面结构（$\mathrm{\Delta }$24 = 0.003-0.021 埃并且$\mathrm{\Delta }$C${}_{\beta }$= 0.004−0.041 Å)，复合 ZnTPF 的单晶数据也证实了这一点${}_{20}$P, 7 显示了平面几何形状，而 Fe 和 Mn 配合物显示出轻微的非平面结构（$\mathrm{\Delta }$24 = 0.101–0.143 埃并且$\mathrm{\Delta }$C${}_{\beta }$= 0.080–0.112 Å)，正如密度泛函理论 (DFT) 计算所揭示的那样，由于它们的轴向位点被 −Cl 配体占据，因此它们发生了扭曲。此外，电子光谱显示按照 NiTPF 的顺序逐渐发生红移${}_{20}$P<CoTPF${}_{20}$P < 铜TPF${}_{20}$PCl < H ₂ TPF${}_{20}$P=铁TPF${}_{20}$PCl < ZnTPF${}_{20}$P < 锰TPF${}_{20}$PCl是通过在卟啉核心附加不同的金属离子而形成的。锰TPF${}_{20}$PCl 表现出最显着的红移（$\mathrm{\Delta }{\lambda }_{\text{最大限度}}$= 63 nm) 在 Soret 波段与 H ₂ TPF相比${}_{20}$P. 另外，MnTPF${}_{20}$PCl 和 FeTPF${}_{20}$由于金属之间的相互作用，PCl 在 364 和 345 nm 附近显示出独特的分裂 Soret 谱带图案$d$-轨道和周围的配体。Zn的填充3d轨道的电化学氧化还原电位赋予ZnTPF${}_{20}$P（环中心）具有最低的氧化电位。