Metal Complexes of 5,15‐Porphyrinquinones: Systematic Study of Crystal Structure, Electronic Structure, and Lewis Acidity,European Journal of Inorganic Chemistry

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Metal Complexes of 5,15‐Porphyrinquinones: Systematic Study of Crystal Structure, Electronic Structure, and Lewis Acidity
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-06-09 , DOI: 10.1002/ejic.202000527
Ken-ichi Yamashita _{1,

2} , Daisuke Hirano ₁ , Ken-ichi Sugiura ₁

Affiliation

We conducted the first systematic study on the synthesis, structure, and properties of various divalent metal complexes (Ni^II, Cu^II, Zn^II, Pd^II, Pt^II, and Pb^II) of 5,15‐porphyrinquinone (PQ, a quinone compound of porphyrin) for diversifying the chemistry of traditional quinone‐metal complexes. Similar to electron‐accepting nature of PQ, the metal complexes studied here also exhibit it. Ni^II, Pd^II, and Pt^II complexes favor face‐to‐face stacked structures in the crystals, thus inducing effective Pt^II–Pt^II interaction, which has not been observed in the porphyrin analogues to date. Ultraviolet‐visible (UV/Vis) absorption spectra of the metal complexes vary widely depending on the metal ion and owing to the effective d(metal)–π(PQ) coupling in their molecular orbitals. Quantitative analyses of the axial ligation on the central metal ions (Ni^II and Cu^II) revealed significantly larger binding constants than those of the porphyrin analogues, indicating significant enhancement of their Lewis acidities due to the strong electron‐withdrawing nature of PQ.

中文翻译：

5,15-卟啉醌的金属配合物：晶体结构，电子结构和路易斯酸度的系统研究

我们对5,15-卟啉醌（PQ，醌）的各种二价金属络合物（Ni ^II，Cu ^II，Zn ^II，Pd ^II，Pt ^II和Pb ^II）的合成，结构和性质进行了首次系统研究卟啉化合物），以使传统的醌金属配合物的化学性质多样化。与PQ的电子接受性质相似，此处研究的金属络合物也表现出它。Ni ^II，Pd ^II和Pt ^II络合物有利于晶体中面对面的堆叠结构，从而诱导出有效的Pt ^II –Pt ^II相互作用，迄今为止在卟啉类似物中尚未观察到。金属络合物的紫外可见（UV / Vis）吸收光谱因金属离子的不同而有很大差异，这归因于分子轨道中有效的d（金属）-π（PQ）耦合。中心金属离子（Ni ^II和Cu ^II）上轴向连接的定量分析显示，结合常数比卟啉类似物的结合常数大得多，这表明由于PQ具有很强的吸电子特性，其路易斯酸度显着提高。

更新日期：2020-06-09

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