Dinuclear ruthenium bipyridine complexes with a bis(iminodioxolene)-meta-phenylene ligand: magnetic coupling and mixed valence character of the semiquinonato species

De Biani FF; Dei A; Sangregorio C; Sorace L

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Dinuclear ruthenium bipyridine complexes with a bis(iminodioxolene)-meta-phenylene ligand: magnetic coupling and mixed valence character of the semiquinonato species

机译：具有双（亚氨基二氧杂环戊烯）-间亚苯基的配体的双核钌联吡啶配合物：半喹诺酮物种的磁耦合和混合价态特征

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The dinuclear bis-iminosemiquinonato [Ru(bpy)(2)(L)(2)Ru(bpy)(2)](PF6)(2) complex where L is the deprotonated form of N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine (H4L), has been synthesised. For comparison purposes, the mononuclear iminosemiquinonato [Ru(bpy)(2)L']PF6 formed by the N-phenyl-o-aminophenol (H2L') was also investigated. Magnetic investigation evidences that the bis-semiquinonato species is characterised by a moderately strong ferromagnetic interaction (H = JS(1)center dot S-2, J = -85(5) cm(-1)). This result is the theoretically expected one and it is contrasting with the antiferromagnetic interaction observed in previously investigated complexes containing the same ligand. It is suggested that the different behaviour is determined by the different coordination requirements occurring in these complexes. The spectroelectrochemical analysis provides a clear evidence of the valence trapped character of the mono-semiquinonato forms of the ligand. The two mixed valence semiquinonato species containing the quinonato-semiquinonato and semiquinonato-catecholato bridging ligand can be described as class II, but show a significantly different electronic coupling. The electronic factors determining this behaviour are discussed.

机译：双核双亚氨基半醌[Ru（bpy）（2）（L）（2）Ru（bpy）（2）]（PF6）（2）络合物，其中L是N，N'-bis（3，已经合成了5-二叔丁基-2-羟基苯基）-1,3-苯二胺（H4L）。为了比较，还研究了由N-苯基-邻氨基苯酚（H2L'）形成的单核亚氨基半醌[Ru（bpy）（2）L'] PF6。磁性研究表明，bis-semiquinonato物种具有中等强度的铁磁相互作用（H = JS（1）中心点S-2，J = -85（5）cm（-1））。该结果是理论上预期的结果，并且与先前研究的含有相同配体的络合物中观察到的反铁磁相互作用相反。建议不同的行为是由这些复合物中发生的不同协调要求决定的。光谱电化学分析提供了配体的单-半喹诺酮形式的价态捕获特征的清晰证据。包含喹啉酮-半喹啉酮和半喹啉酮-邻苯二酚桥联配体的两种混合价半喹啉酮物质可描述为II类，但显示出显着不同的电子耦合。讨论了决定这种行为的电子因素。

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《Dalton transactions: An international journal of inorganic chemistry》 |2005年第24期|共6页
作者
De Biani FF; Dei A; Sangregorio C; Sorace L;
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正文语种 eng
中图分类无机化学;
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AB-INITIO CALCULATIONS; SPIN GROUND-STATES; METAL-COMPLEXES; ELECTRONIC-STRUCTURE; BRIDGING LIGANDS; REDOX; TRANSITION; QUINONE; SERIES; ION;

机译：绝对值计算;自旋基态;金属络合物;电子结构;桥接配体;氧化还原;转变;醌;系列;离子;

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1. Dinuclear ruthenium bipyridine complexes with a bis(iminodioxolene)-meta-phenylene ligand: magnetic coupling and mixed valence character of the semiquinonato species [J] . De Biani FF, Dei A, Sangregorio C, Dalton transactions: An international journal of inorganic chemistry . 2005,第24期

机译：具有双（亚氨基二氧杂环戊烯）-间亚苯基的配体的双核钌联吡啶配合物：半喹诺酮物种的磁耦合和混合价态特征
2. PROTON-INDUCED TUNING OF ELECTROCHEMICAL AND PHOTOPHYSICAL PROPERTIES IN MONONUCLEAR AND DINUCLEAR RUTHENIUM COMPLEXES CONTAINING 2,2'-BIS(BENZIMIDAZOL-2-YL)-4,4'-BIPYRIDINE - SYNTHESIS, MOLECULAR STRUCTURE, AND MIXED-VALENCE STATE AND EXCITED-STATE [J] . Haga MA., Koseki S., Fujimoto K., Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 1996,第11期

机译：质子诱导的含2,2'-BIS（苯并咪唑-2-基）-4,4'-联吡啶-合成，分子结构和混合价态的单核和小核钌配合物的电化学和光物理性质的调节州
3. PROTON-INDUCED TUNING OF ELECTROCHEMICAL AND PHOTOPHYSICAL PROPERTIES IN MONONUCLEAR AND DINUCLEAR RUTHENIUM COMPLEXES CONTAINING 2,2'-BIS(BENZIMIDAZOL-2-YL)-4,4'-BIPYRIDINE - SYNTHESIS, MOLECULAR STRUCTURE, AND MIXED-VALENCE STATE AND EXCITED-STATE [J] . Haga MA., Koseki S., Fujimoto K., Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 1996,第11期

机译：质子诱导的含2,2'-BIS（苯并咪唑-2-基）-4,4'-联吡啶-合成，分子结构和混合价态的单核和小核钌配合物的电化学和光物理性质的调节州
4. SERR, FT-Raman, and FT-IR Spectroscopies of Mono- and Dinuclear Ruthenium(II) Bipyridine Complexes with 1,4-Bis ([1,10]Phenanthroline-[5,6-D]Imidazol-2-Yl)Benzene Ligand [C] . Xiao-Yuan Li International conference on Raman spectroscopy;ICORS 2000 . 2000

机译：具有1,4-双（[1,10] Phenanthroline- [5,6-D] Imidazol-2-Yl）苯的单核和双核钌（II）联吡啶配合物的SERR，FT-Raman和FT-IR光谱配体
5. Ruthenium complexes of quinone-related ligands: A study of the redox states of ruthenium(II)bis(2,2' bipyridine)-2-aminothiophenol. [D] . Ebadi, Mehrdad. 1997

机译：醌相关配体的钌配合物：钌（II）双（2,2'联吡啶）-2-氨基硫酚的氧化还原态研究。
6. One-Pot Self-Assembly of Dinuclear Tetranuclear and H-Bonding-Directed Polynuclear Cobalt(II) Cobalt(III) and Mixed-Valence Co(II)/Co(III) Complexes of Schiff Base Ligands with Incomplete Double Cubane Core [O] . Santokh S. Tandon, Neil Patel, Scott D. Bunge, 2020

机译：二核四核和H键合的多核钴（II）钴（III）和混合价CO（II）/ CO（III）复合物的单核四核和H键合的多核钴（II）具有不完全的双副Cubane核
7. cis-Bis(2,2′-bipyridine-κ2N,N′)bis(pyridin-4-amine-κN1)ruthenium(II) bis(hexafluoridophosphate) acetonitrile monosolvatePart II. Ruthenium(II) coordination complexes with 4-aminopyridine and α-diimine ligands. [O] . Mariana R. Camilo, Felipe T. Martins, Valé, 2013

机译：顺式 - 双（2,2＆＃8242; - 联吡啶 - ＆＃954; 2N，N＆＃8242;）双（吡啶-4-胺 - ＆＃954; N1）钌（II）双（六氟磷酸）乙腈单溶剂化物II。钌（II）与4-氨基吡啶和＆＃945-二亚胺配体配位。
8. Electropolymerization of Ruthenium Bis(1,10-phenanthroline)(4-methyl-4'vinyl-2,2'-bipyridine) Complexes through Direct Attack on the Ligand Ring System [R] . Guarr, T. F., Anson, F. C. 1987

机译：直接攻击配体环系统对双（1,10-菲咯啉）（4-甲基-4'-乙烯基-2,2'-联吡啶）配合物的电聚合

Dinuclear ruthenium bipyridine complexes with a bis(iminodioxolene)-meta-phenylene ligand: magnetic coupling and mixed valence character of the semiquinonato species

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