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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ligand recruitment and spin transitions in the solid-state photochemistry of Fe ~(III)TPPCl
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Ligand recruitment and spin transitions in the solid-state photochemistry of Fe ~(III)TPPCl

机译：Fe〜（III）TPPC1固态光化学中的配体募集和自旋转变

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摘要

We report evidence for the formation of long-lived photoproducts following excitation of iron(III) tetraphenylporphyrin chloride (Fe ~(III)TPPCl) in a 1:1 glass of toluene and CH _2Cl _2 at 77 K. The formation of these photoproducts is dependent on solvent environment and temperature, appearing only in the presence of toluene. No long-lived product is observed in neat CH _2Cl _2 solvent. A 2-photon absorption model is proposed to account for the power-dependent photoproduct populations. The products are formed in a mixture of spin states of the central iron(III) metal atom. Metastable six-coordinate high-spin and low-spin complexes and a five-coordinate high-spin complex of iron(III) tetraphenylporphyrin are assigned using structure-sensitive vibrations in the resonance Raman spectrum. These species appear in conjunction with resonantly enhanced toluene solvent vibrations, indicating that the Fe ~(III) compound formed following photoexcitation recruits a toluene ligand from the surrounding environment. Low-temperature transient absorption (TA) measurements are used to explain the dependence of product formation on excitation frequency in this photochemical model. The six-coordinate photoproduct is initially formed in the high-spin Fe ~(III) state, but population relaxes into both high-spin and low-spin state at 77 K. This is the first demonstration of coupling between the optical and magnetic properties of an iron-centered porphyrin molecule.
机译：我们报告了在77 K下在1：1的甲苯和CH _2Cl _2玻璃中激发四价铁氯化铁（III）四苯基卟啉氯化铁（Fe〜（III）TPPCl）后形成长寿命光产物的证据。这些光产物的形成是取决于溶剂环境和温度，仅在甲苯存在下出现。在纯CH _2Cl _2溶剂中未观察到长寿命产物。提出了一个2-光子吸收模型来解释功率相关的光产物种群。产物以中心铁（III）金属原子的自旋态混合物形成。使用共振拉曼光谱中的结构敏感振动分配了亚铁四苯基卟啉亚稳态的六坐标高旋转和低旋转复合物以及五坐标高旋转复合物。这些物质与共振增强的甲苯溶剂振动一起出现，表明光激发后形成的Fe〜（III）化合物从周围环境中吸收了甲苯配体。低温瞬态吸收（TA）测量用于解释该光化学模型中产物形成对激发频率的依赖性。六坐标光产物最初以高自旋Fe〜（III）态形成，但种群在77 K时弛豫到高自旋和低自旋态。这是光与磁特性之间耦合的第一个证明。以铁为中心的卟啉分子。

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