Proton-induced switching of metal-metal interactions in dinuclear ruthenium and osmium complexes bridged by 2,2'-bis(2-pyridyl)bibenzimidazole

Haga, Masa‐aki; Ano, Tomo-aki; Kano, Kenji; Yamabe, Shinichi

doi:10.1021/ic00020a014

Cited by 150 publications

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“…It shows that the deprotonation of the coordinated bbpaH ligand can shift the redox potential of the ruthenium centre by 430 mV, which is larger than the shift (ca. 300-350 mV per proton) of the redox potentials reported for ruthenium, osmium and iron complexes with the ligands bearing multi-imidazolyl and -benzimidazolyl units, [9,[14][15][16] but similar to the shift (350-420 mV) of the Ru II /Ru III oxidation potentials reported for monoruthenium complexes with two bpy ligands and one triazole-or pyrazole-containing ligand. [21,23,29,30] …”

Section: Resultssupporting

confidence: 69%

“…[10][11][12] The effect of the distal deprotonation of the ligands bearing imidazole and benzimidazole units on the physical and chemical properties of mono-and dinuclear ruthenium and osmium complexes has been reported. [13][14][15][16][17][18][19] In addition to the imidazole-containing ligands, mono-and dinuclear ruthenium complexes with ligands bearing triazole and pyrazole units were also extensively studied for their interesting electrochemical and photophysical properties. [20][21][22][23][24] In this communication, we …”

Section: Introductionmentioning

confidence: 99%

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Effect of Deprotonation of a Benzimidazolyl Ligand on the Redox Potential and the Structures of Mononuclear Ruthenium(II) Complexes

et al. 2007

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Section: Resultssupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Effect of Deprotonation of a Benzimidazolyl Ligand on the Redox Potential and the Structures of Mononuclear Ruthenium(II) Complexes

et al. 2007

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“…Unlike pyridine and pyrazine ligands, which have low-lying π-orbitals, and therefore act as π-acceptor ligands, the triazolate derivatives are similar to imidazoles and behave as σ/π-donors. 44,45 This means that the metal-metal electronic communication is governed predominantly by a hole-transfer mechanism. 46 As a consequence, protonation of the benzotriazolate ligand induces a decrease of its π-orbital energies, and the interaction between the dπ(Ru) and π(btaH) orbitals decreases, leading to the lowering of the resonance energy.…”

Section: Proton-induced Molecular Switchingmentioning

confidence: 99%

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

Toma

2004

ChemInform

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Neste limiar da era nanotecnológica, o planejamento molecular dos materiais e os estudos de moléculas isoladas estão abrindo imensas possibilidades no emprego de sistemas moleculares em dispositivos eletrônicos e fotônicos, bem como em aplicações tecnológicas baseadas em propriedades de chaveamento ou reconhecimento molecular. Com esse escopo, os químicos inorgânicos em particular, podem aplicar com vantagens as estratégias proporcionadas pela química de coordenação, para construir nanomateriais funcionais que permitam a exploração das propriedades dos centros metálicos e das características dos ligantes presentes. A química de coordenação também oferece recursos eficientes na auto-montagem de nanoestruturas, baseadas na especificidade da interação metal-ligante e nas características estereoquímicas dos complexos. Diversos materiais moleculares gerados a partir de compostos inorgânicos e metal-orgânicos são focalizados neste artigo, com ênfase em novas porfirinas e porfirazinas supramoleculares, clusters e complexos metálicos. Tais sistemas também são enfocados sob o ponto de vista de suas aplicações em catálise, sensores e dispositivos moleculares.At the onset of the nanotechnology age, molecular designing of materials and single molecule studies are opening wide possibilities of using molecular systems in electronic and photonic devices, as well as in technological applications based on molecular switching or molecular recognition. In this sense, inorganic chemists are privileged by the possibility of using the basic strategies of coordination chemistry to build up functional supramolecular materials, conveying the remarkable chemical properties of the metal centers and the characteristics of the ancillary ligands. Coordination chemistry also provides effective self-assembly strategies based on specific metal-ligand affinity and stereochemistry. Several molecular based materials, derived from inorganic and metal-organic compounds are focused on this article, with emphasis on new supramolecular porphyrins and porphyrazines, metal-clusters and metal-polyimine complexes. Such systems are also discussed in terms of their applications in catalysis, sensors and molecular devices.

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“…[5,6] However, when the bridging ligand becomes longer, metal-to-metal interactions can become more elusive, hence difficult to characterize. [7,8] Most of the time, long-distance metal-tometal interactions are transmitted through conjugated π systems like polyalkene, [9][10][11][12] polyalkyne, [13,14] or polyphenylene [15][16][17][18][19] ligands. Typically, both metal fragments can be connected to the bridging ligand in an axial, η 1 ,η 1 fashion, and interact across the organic manifold through the conjugated π system (Scheme 1, a).…”

Section: Introductionmentioning

confidence: 99%

Ruthenium‐to‐Platinum Interactions in η⁶,η¹ NCN‐Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical Study

et al. 2010

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A series of η6,η1‐heterobimetallic complexes have been prepared in which a [Ru(η6‐arene)(C5R5)]+ fragment (R = H or Me) and an η1‐NCN‐pincer platinum fragment are combined within the same molecule. In complexes [2]+ and [3]+, the ruthenium and platinum centers are η6 and η1 coordinated, respectively, to the same arene ring, whereas in [4A]+ and [5A]+ they are coordinated to two different arene rings that are linked with a covalent bond ([4A]+) or an ethyl bridge ([5A]+). Upon changing the organic manifold between both metal centers, very strong ([2]+) to very weak ([5A]+) ruthenium‐to‐platinum interactions are obtained. Experimentally, X‐ray crystal structures show an increaing steric hindrance when the Ru–Pt distance diminishes, and electrochemical and 195Pt NMR spectroscopic studies show a decreasing electron density on platinum from [5A]+ to [2]+. Theoretical DFT calculations were undertaken, which show an increasing charge on platinum from [5A]+ to [2]+. Our theoretical analysis shows that the particularly strong ruthenium‐to‐platinum electronic interactions in [2]+ and [3]+ do not come from binding of ruthenium to platinum, but from the pincer Cipso sharing its electron density between both metal centers, which decreases the σ donation to platinum, and from increased backdonation of the platinum d electrons into the π system of the arene ring.

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Proton-induced switching of metal-metal interactions in dinuclear ruthenium and osmium complexes bridged by 2,2'-bis(2-pyridyl)bibenzimidazole

Cited by 150 publications

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Effect of Deprotonation of a Benzimidazolyl Ligand on the Redox Potential and the Structures of Mononuclear Ruthenium(II) Complexes

Effect of Deprotonation of a Benzimidazolyl Ligand on the Redox Potential and the Structures of Mononuclear Ruthenium(II) Complexes

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

Ruthenium‐to‐Platinum Interactions in η⁶,η¹ NCN‐Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical Study

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Proton-induced switching of metal-metal interactions in dinuclear ruthenium and osmium complexes bridged by 2,2'-bis(2-pyridyl)bibenzimidazole

Cited by 150 publications

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Effect of Deprotonation of a Benzimidazolyl Ligand on the Redox Potential and the Structures of Mononuclear Ruthenium(II) Complexes

Effect of Deprotonation of a Benzimidazolyl Ligand on the Redox Potential and the Structures of Mononuclear Ruthenium(II) Complexes

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

Ruthenium‐to‐Platinum Interactions in η6,η1 NCN‐Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical Study

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Ruthenium‐to‐Platinum Interactions in η⁶,η¹ NCN‐Pincer Arene Heterobimetallic Complexes: An Experimental and Theoretical Study