Synthesis, electronic and photophysical investigations of ruthenium(II)-centred heterometallic Kuratowski complexes which feature redox-active metal centres

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-04-02 DOI:10.1039/d5dt00088b

Wiebke G. Rehfuß, Andreas Kalytta-Mewes, Maryana Kraft, Binh Minh Nguyen, Wolfgang Brütting, Dirk Volkmer

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Abstract

We present the synthesis and comprehensive characterization of a series of complexes belonging to the Kuratowski (K_3,3) family. These are pentanuclear {Ru^IIM₄} complexes (M = Co²⁺, Ni²⁺, Zn²⁺) which were prepared by employing a directed two-step synthesis facilitated by the recently published [Ru^II(Me₂bta)₂(Me₂btaH)₄] precursor complex (Me₂btaH = 5,6-dimethyl-1,2,3-benzotriazole). The pentanuclear Kuratowski complexes showcase a unique combination of photo-active ruthenium with redox-active metal centres. The μ₃-bridging 1,2,3-triazolate ligands in these complexes facilitate electronic coupling between the metal centers, as revealed through electrochemical and photophysical studies. Comparisons with {Ru^IIZn₄} and {Ru^IICu₄} Kuratowski compounds reveal that Co(II) significantly influences both the Ru(II/III) redox step and the position of the MLCT (metal-to-ligand charge transfer) band, whereas Cu(II) and Ni(II) exhibit minimal influence. Photophysical investigations reveal the {Ru^IIZn₄} compound as the only phosphorescent species, displaying an emission band extending into the near-infrared region. This emission originates from a triplet ³MLCT state and features an exceptionally large Stokes shift, with a long lifetime of the excited-state of about 3.3 μs in powdered form at room temperature.

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以氧化还原活性金属中心为特征的钌(II)中心异金属库拉托夫斯基配合物的合成、电子和光物理研究

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.