Aerial carbon dioxide conversion to carbonate mediated by a lead(II) complex with tridentate bipyridine containing a hydrazide ligand under electrochemical conditions yielding single-component white-light-emitting phosphors,Inorganic Chemistry Frontiers

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Aerial carbon dioxide conversion to carbonate mediated by a lead(II) complex with tridentate bipyridine containing a hydrazide ligand under electrochemical conditions yielding single-component white-light-emitting phosphors
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2024-07-23 , DOI: 10.1039/d4qi01323a
Ghodrat Mahmoudi _{1,

2,

3} , Isabel Garcia-Santos ₄ , Elena Labisbal ₄ , Alfonso Castiñeiras ₄ , Vali Alizadeh ₅ , Rosa M. Gomila ₆ , Antonio Frontera ₆ , Damir A. Safin _{7,

8}

Affiliation

A novel tetranuclear complex [Pb₄L₄(CO₃)₂]·4H₂O (1·4H₂O) is reported, which was obtained through the electrochemical oxidation of a lead anode under an ambient atmosphere in a CH₃CN : MeOH solution of N’-isonicotinoylpicolinohydrazonamide (HL). CO₃²⁻ anions were formed through the conversion of aerial CO₂ via the Pb²⁺–L complex system under electrochemical conditions. The ligand L links two Pb²⁺ cations through the carbonyl oxygen atom, while the CO₃²⁻ anion links two Pb²⁺ cations through two monodentate and one bidentate oxygen atoms. The molecular structure of 1 is stabilized by a pair of Pb⋯O tetrel bonds formed with the bidentate oxygen atom of the CO₃²⁻ anion, while molecules of 1 are interlinked through reciprocal π(chelate ring)⋯π(chelate ring), π(chelate ring)⋯π(noncovalent ring) and Pb⋯π(noncovalent ring) interactions, yielding a 1D supramolecular chain. The same reaction but under a nitrogen atmosphere yielded a novel mononuclear complex [PbL₂]·MeOH·2H₂O (2·MeOH·2H₂O). In the structure of 2, each ligand L exhibits a tridentate coordination mode. Molecules of 2 are also interlinked through reciprocal π(chelate ring)⋯π(chelate ring), π(chelate ring)⋯π(noncovalent ring) and Pb⋯π(noncovalent ring) interactions, similar to 1, yielding a 1D supramolecular chain. The energetic features of these assemblies were studied using DFT calculations. Additionally, QTAIM analysis was employed to characterize noncovalent contacts, including intermolecular Pb⋯N tetrel bonds. These tetrel bonds were further analyzed using the ELF and Laplacian of electron density 2D maps, which confirmed their noncovalent nature. The optical properties of the complexes were revealed using UV–vis and diffuse reflectance spectroscopy and spectrofluorometry. Both complexes were found to be emissive in a solution of MeOH. CIE-1931 chromaticity coordinates of (0.38, 0.37) and (0.31, 0.32) for 1·4H₂O and 2·MeOH·2H₂O, respectively, fall within the white gamut of the chromaticity diagram.

中文翻译：

在电化学条件下，由铅（II）与含有酰肼配体的三齿联吡啶络合物介导的空气二氧化碳转化为碳酸盐，产生单组分白光发射磷光体

报道了一种新型四核配合物[Pb ₄ L ₄ (CO ₃ ) ₂ ]·4H ₂ O ( 1 ·4H ₂ O)，它是通过铅阳极在CH ₃ CN中的环境气氛下电化学氧化获得的： N'-异烟酰吡啶甲肼酰胺 ( HL ) 的甲醇溶液。 CO ₃ ²⁻阴离子是在电化学条件下通过Pb ²⁺ - L复合体系将空气中的CO ₂转化而形成的。配体L通过羰基氧原子连接两个Pb ²⁺阳离子，而CO ₃ ²⁻阴离子通过两个单齿和一个二齿氧原子连接两个Pb ²⁺阳离子。 1的分子结构通过与CO ₃ ²⁻阴离子的二齿氧原子形成的一对Pb⋯O四键稳定，而1的分子通过互惠的π（螯合环）⋯π（螯合环）相互连接， π（螯合环）⋯π（非共价环）和Pb⋯π（非共价环）相互作用，产生一维超分子链。在氮气气氛下进行相同的反应，得到新型单核配合物[PbL ₂ ]·MeOH·2H ₂ O ( 2 ·MeOH·2H ₂ O)。在2的结构中，每个配体L表现出三齿配位模式。 2的分子也通过相互的 π（螯合环）⋯π（螯合环）、π（螯合环）⋯π（非共价环）和 Pb⋯π（非共价环）相互作用相互连接，类似于1 ，产生一维超分子链。使用 DFT 计算研究了这些组件的能量特征。此外，还采用 QTAIM 分析来表征非共价接触，包括分子间 Pb⋯N tetrel 键。使用电子密度二维图的 ELF 和拉普拉斯算子进一步分析了这些四键，证实了它们的非共价性质。使用紫外可见光谱、漫反射光谱和荧光分光光度法揭示了复合物的光学性质。发现两种配合物在甲醇溶液中均具有发射性。 1 ·4H ₂ O和2 ·MeOH·2H ₂ O的CIE-1931色品坐标分别为(0.38,0.37)和(0.31,0.32)，落在色品图的白色域内。

更新日期：2024-07-23

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