Transient Absorption Spectra of Metal‐Free and Transition‐Metal 5,10,15,20‐Tetraferrocene Porphyrins: Influence of the Central Metal Ion, Solvent Polarity, and the Axial Ferrocene Ligand
Transient Absorption Spectra of Metal‐Free and Transition‐Metal 5,10,15,20‐Tetraferrocene Porphyrins: Influence of the Central Metal Ion, Solvent Polarity, and the Axial Ferrocene Ligand
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金属—游离态和过渡态—金属 5、10、15、20—四二茂铁卟啉的瞬态吸收光谱：中心金属离子、溶剂极性和轴向二茂铁配体的影响
DOI：
10.1002/ejic.202101007
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发表时间：
2022
影响因子：
2.3
通讯作者：
Nemykin, Victor N.
中科院分区：
文献类型：
--
作者：
Schrage, Briana R.;Ermilov, Eugeny;Nemykin, Victor N.
研究了H2 TFcP、ZnTFcP、PdTFcP和FcInTFcP系列抗磁性化合物（TFcP（2-）= 5，10，15，20-四二茂铁卟啉二价阴离子）在极性溶剂（DMF）和非极性溶剂（甲苯）中的瞬态吸收光谱。 电荷分离的（Fc+-卟啉-）的形成和失活。在所有情况下都观察到了状态。电荷分离态的寿命对所有化合物来说几乎是恒定的（约20 ps），并且与中心离子和溶剂的性质无关。 在所有配合物中均未观察到三重态的形成。在极性DMF溶剂中观察到第三种次要的长寿命（160-480 ps）组分。该组分被暂时指定为与DMF中的羰基氧弱结合的卟啉物种。对目标化合物的基态、激发态和三重态进行了密度泛函理论（DFT）和时域密度泛函理论（TDDFT）的计算，结果与实验数据一致。
The transient absorption spectra of the series of diamagnetic H2TFcP, ZnTFcP, PdTFcP, and FcInTFcP compounds (TFcP(2‐)=5,10,15,20‐tetraferroceneporphyrin dianion) were investigated in polar (DMF) and non‐polar (toluene) solvents using excitation at 650 nm. The formation and the deactivation of the charge‐separated (Fc+‐Porphyrin−.) state were observed in all cases. The lifetime of the charge‐separated state is nearly constant for all compounds (∼20 ps) and independent of the nature of the central ion and solvent. The formation of the triplet state in all the complexes was not observed. The third, minor long‐lived (160–480 ps) component was observed in polar DMF solvent. This component was tentatively assigned to the porphyrin species that are weakly bound to the carbonyl oxygen in DMF. DFT and TDDFT calculations on the ground state, excited state, and triplet state of the target compounds were in agreement with the experimental data.