Paddlewheel-Type Diruthenium(II,II) Naphthyridine Complexes with π-Conjugated Aromatic Carboxylate Ligands

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2025-06-09 DOI:10.1021/acs.cgd.5c0036510.1021/acs.cgd.5c00365

Nozomi Tada, Natsumi Yano, Yoshiki Mizogami, Kanami Matsubara, Makoto Handa* and Yusuke Kataoka*,

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引用次数: 0

Abstract

Three heteroleptic diruthenium (Ru₂) complexes bridged by 1,8-naphtyridine-2-carboxylate (npc) and π-conjugated aromatic carboxylate ligands, [Ru₂(npc)₂(O₂CNap)₂] (3; ^–O₂CNap = 1-naphthalenecarboxylate), [Ru₂(npc)₂(O₂CAnt)₂] (4; ^–O₂CAnt = 9-anthracenecarboxylate), and [Ru₂(npc)₂(O₂CPyr)₂] (5; ^–O₂CPyr = 1-pyrenecarboxylate), were prepared by carboxylate–exchange reactions of [Ru₂(npc)₂(O₂CMe)₂] (1) with the corresponding carboxylic acids. Paramagnetic ¹H NMR, ESI-MS, elemental analyses, and single crystal X-ray diffraction analyses revealed that the molecular structures of 3–5 form a “paddlewheel-type” structure, in which two npc and two aromatic carboxylate ligands were coordinated to a Ru₂ core with a cis–2:2-arrangement. Variable-temperature magnetic susceptibility measurements of 3–5 showed large zero-field splitting of the triplet ground state of the Ru₂⁴⁺ core (D = 250, 270, and 257 cm^–1, respectively). Density functional theory calculations revealed that the electronic configuration of the Ru₂ core in 3–5 was π⁴δ²σ²δ*²π*², which was the same configuration as that of [Ru₂(npc)₂(O₂CPh)₂] (2; ^–O₂CPh = benzoate). The absorption spectra of 3–5 in DMF showed the intense visible absorption bands at 500–800 nm, which were due to the metal–to–ligand charge transfer (MLCT) from the Ru₂ core to the npc ligands. The cyclic voltammetry diagrams of 3–5 exhibited two reversible reduction waves and one reversible oxidation wave, corresponding to the reduction of two npc ligands and the oxidation of the Ru₂ core, respectively.

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与π共轭芳羧酸配体的桨轮型二钌（II，II）萘配合物

由1,8-萘啶-2-羧酸酯（npc）和π共轭芳羧酸酯配体桥接的三种杂电性二钌（Ru2）配合物[Ru2(npc)2(O2CNap)2] (3；-O2CNap = 1-萘甲酸酯),[Ru2(npc)2(o2can)2] (4；[Ru2(npc)2(O2CPyr)2] (5；[Ru2(npc)2(O2CMe)2](1)与相应的羧酸进行羧酸交换反应，制得-O2CPyr = 1-芘羧酸酯。顺磁1H NMR、ESI-MS、元素分析和单晶x射线衍射分析表明，3-5的分子结构为“桨轮型”结构，其中2个npc和2个芳香羧酸配体以顺式2:2排列在一个Ru2核上。3-5的变温磁化率测量表明，Ru24+磁芯的三态基态存在较大的零场分裂（D分别为250、270和257 cm-1）。密度泛函理论计算表明，3-5中Ru2核的电子构型为π4δ2σ2δ*2π*2，与[Ru2(npc)2(O2CPh)2](2)的电子构型相同；-O2CPh =苯甲酸盐)。3-5在DMF中的吸收光谱在500-800 nm处显示出较强的可见吸收带，这是由于金属-配体电荷转移（MLCT）从Ru2核转移到npc配体。3 ~ 5的循环伏安图表现为两个可逆还原波和一个可逆氧化波，分别对应于两个npc配体的还原和Ru2核的氧化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.