Different Degrees of Electron Delocalization in Mixed Valence Ru‐Ru‐Ru Compounds by Cyanido‐/Isocyanido‐Bridge Isomerism

Yang, Yuying; Zhu, Xiaofang; Hu, Shengmin; Su, Shao‐Dong; Zhang, Lintao; Wen, Yuh‐Sheng; Wu, Xintao; Sheng, Tianlu

doi:10.1002/anie.201806157

Cited by 32 publications

(40 citation statements)

References 59 publications

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“…The trinuclear ruthenium compound [Cp*(dppe)Ru II –(µ‐NC)–Ru II (dmap) 4 –(µ‐CN)–Ru II (dppe)Cp*] 2+ where dmap = dimethylamino pyridine and cyanide is linked by carbon to the central ruthenium, has been prepared by Sheng et al, together with the linkage isomer where the bridging cyanides are linked by nitrogen to the central ruthenium. [27a] Upon oxidation of the first isomer, the terminal rutheniums are oxidized first and the one‐electron product present a sharp band at 5000 cm –1 , assigned to an intervalence band between the outer ruthenium atoms. The system would be a class III system with extensive delocalization on all the trimetallic squeletton.…”

Section: Some Original Structuresmentioning

confidence: 99%

“…A similar situation was encountered in the earlier trimetallic system [Cp(dppe)Fe II –(µ‐NC)–Ru II (phen) 2 –(µ‐CN)–Fe II (dppe)Cp] 2+ where phen = orthophenanthroline. [27b] There are two possible isomers, cis and trans , corresponding to the disposition of the cyanide ligands on the central metal. Here also, the outer metals are oxidized first.…”

Section: Some Original Structuresmentioning

confidence: 99%

“…Many mixed‐valence studies have used DFT to interpret experimental results, with compounds as diverse as Ru dimers with quinonoid bridge, Ru dimers with diethynyl bridges,[41a] or other carbon‐rich bridges,[19a], Ru‐amine‐Ru systems,[9b] Ru trimers linked by cyanide bridges,[27a] etc. In most of the above papers, DFT is used in conjunction with Kohn–Sham orbitals to discuss spin density, electronic spectra, or EPR parameters, but generally without theoretical determination of the ground state geometry, and in particular its symmetry.…”

Section: Theoretical Descriptionsmentioning

confidence: 99%

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Mixed‐Valent Compounds and their Properties – Recent Developments

Launay

2019

Eur J Inorg Chem

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Recent evolutions, essentially in the last 15 years, are reviewed in the field of molecular mixed-valent compounds and their properties. The considered systems are of the type M n -BL-M n where M n is either a monometallic terminal site (n = 1) or a polymetallic cluster (n = 2, 3), and BL is a bridging ligand. A large variety of bridging ligands is considered: non-innocent, long conjugated, ambidentate, cross-conjugated, H-bonded, switching. The theoretical descriptions are briefly reviewed and [a]

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Section: Some Original Structuresmentioning

confidence: 99%

Section: Some Original Structuresmentioning

confidence: 99%

Section: Theoretical Descriptionsmentioning

confidence: 99%

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Mixed‐Valent Compounds and their Properties – Recent Developments

Launay

2019

Eur J Inorg Chem

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“…In recent years, the field of molecule electronics has attracted the attention of scientists owing to the great potential for a further drop in device dimensions. Multiple redox‐active compounds have widely been explored for applications in molecular electronics technology and information storage, and as molecular wires in a mixed‐valence state . A wide range of bridged diruthenium(II) complexes belonging to the latter family have been thoroughly explored owing to their facile accessibility and high stability.…”

Section: Introductionmentioning

confidence: 99%

Electronic Properties of Oxidized Cyclometalated Diiridium Complexes: Spin Delocalization Controlled by the Mutual Position of the Iridium Centers

Zhang

et al. 2020

Chemistry A European J

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Four cyclometalated diiridium complexes, with IrCp*Cl (Cp*=η5‐C5Me5−) termini bridged by 1,4‐ and 1,3‐bis(p‐tolyliminoethyl)benzene (1, 2), or 1,4‐ and 1,3‐bis(2‐pyridyl)benzene (3, 4), were prepared and characterized by nuclear magnetic resonance (NMR) spectroscopy and single‐crystal X‐ray diffraction (complexes 1, 2, and 4). The two iridium centers in complexes 1 and 3 are thus bound at the central benzene ring in the para‐position (trans‐Ir2), whereas those in complexes 2 and 4 are in the meta‐position (cis‐Ir2). Cyclic voltammograms of all four complexes show two consecutive one‐electron oxidations. The potential difference between the two anodic steps in 1 and 3 is distinctly larger than that for 2 and 4. The visible–near‐infrared (NIR)–short‐wave infrared (SWIR) absorption spectra of trans‐Ir2 monocations 1+ and 3+ are markedly different from those of cis‐Ir2 monocations 2+ and 4+. Notably, strong near‐infrared electronic absorption appears only in the spectra of 1+ and 3+ whereas 2+ and 4+ absorb only weakly in the NIR‐SWIR region. Combined DFT and TD‐DFT calculations have revealed that (a) 1+ and 3+ (the diiridium‐benzene trans‐isomers) display the highest occupied spin‐orbitals (HOSO) and the lowest unoccupied spin‐orbital (LUSO) evenly delocalized over both molecule halves, and (b) their electronic absorptions in the NIR‐SWIR region are attributed to mixed metal‐to‐ligand and ligand‐to‐ligand charge transfers (MLCT and LLCT). In contrast, cis‐isomers 2+ and 4+ do not feature this stabilizing π‐delocalization but a localized mixed‐valence state showing a weak intervalence charge‐transfer (IVCT) absorption in the SWIR region.

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“…[14] Our group have been focusing on such investigation in cyanido-bridged mixed-valence complexes. [15] Considering [Ru 2 (m-Xap) 4 ] + cluster ions show good redox properties, [12] we attempted to synthesize cyanido-bridged Ru 2…”

mentioning

confidence: 99%

A Diruthenium‐Based Mixed Spin Complex Ru₂⁵⁺(S=1/2)‐CN‐Ru₂⁵⁺(S=3/2)

Zhu

Wen

et al. 2019

Angew Chem Int Ed

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An unusual tetra‐nuclear linear cyanido‐bridged complex [Ru2(μ‐ap)4‐CN‐Ru2(μ‐ap)4](BPh4) (1) (ap=2‐anilinopyridinate) has been synthesized and well characterized. The crystallographic data, magnetic measurement, IR, EPR and theoretical calculation results demonstrate that complex 1 is the first example of mixed spin Ru25+‐based complex with uncommon electronic configurations of S=1/2 for the cyanido‐C bound Ru25+ and S=3/2 for the cyanido‐N bound Ru25+. This phenomenon can be understood by the theoretical calculation results that from the precursor Ru2(μ‐ap)4(CN) (S=3/2) to complex 1 the energy gap between π* and δ* orbitals of the cyanido‐C bound Ru25+ core increases from 0.57 to 1.61 eV due to the enhancement of asymmetrical π back‐bonding effect, but that of the cyanido‐N bound Ru25+ core is essential identical (0.56 eV). Besides, the analysis of UV/Vis‐NIR spectra suggests that there exists metal to metal charge transfer (MMCT) from the cyanido‐N bound Ru25+ (S=3/2) to the cyanido‐C bound Ru25+ (S=1/2), supported by the TDDFT calculations.

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Different Degrees of Electron Delocalization in Mixed Valence Ru‐Ru‐Ru Compounds by Cyanido‐/Isocyanido‐Bridge Isomerism

Cited by 32 publications

References 59 publications

Mixed‐Valent Compounds and their Properties – Recent Developments

Mixed‐Valent Compounds and their Properties – Recent Developments

Electronic Properties of Oxidized Cyclometalated Diiridium Complexes: Spin Delocalization Controlled by the Mutual Position of the Iridium Centers

A Diruthenium‐Based Mixed Spin Complex Ru₂⁵⁺(S=1/2)‐CN‐Ru₂⁵⁺(S=3/2)

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Different Degrees of Electron Delocalization in Mixed Valence Ru‐Ru‐Ru Compounds by Cyanido‐/Isocyanido‐Bridge Isomerism

Cited by 32 publications

References 59 publications

Mixed‐Valent Compounds and their Properties – Recent Developments

Mixed‐Valent Compounds and their Properties – Recent Developments

Electronic Properties of Oxidized Cyclometalated Diiridium Complexes: Spin Delocalization Controlled by the Mutual Position of the Iridium Centers

A Diruthenium‐Based Mixed Spin Complex Ru25+(S=1/2)‐CN‐Ru25+(S=3/2)

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A Diruthenium‐Based Mixed Spin Complex Ru₂⁵⁺(S=1/2)‐CN‐Ru₂⁵⁺(S=3/2)