Metal–metal interactions in dinuclear ruthenium complexes incorporating “stepped-parallel” bridging ligands: synthesis, stereochemistry and intervalence charge transfer

D’Alessandro, Deanna M.; Keene, F. Richard

doi:10.1039/b514111g

Cited by 22 publications

(12 citation statements)

References 47 publications

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“…11 These ligands contain tridentate binding domains arranged in an "angular" fashion. 12 As was previously observed with ligands 3 and 4, 2c the 1 H NMR spectra of these compounds showed significant broadening of the signals of the pyridine protons due to a slow exchange on the NMR timescale of the tautomeric imidazole hydrogens resulting from intramolecular hydrogen bonding to the pyridine ring. We next considered the possibility of extending this ligand design strategy to the preparation of a potentially tetranucleating ligand.…”

Section: Bsupporting

confidence: 67%

“…12 Finally, in order to explore the possibility of tuning the metal-metal interactions in complexes of ligands such as 5, we considered the option of introducing a benzene ring between the fused rings. This proved easier to do with the oxygen, rather than sulfur, analogue and, by reacting 2,5-diaminobenzoquinone 15 with pyridine-2-carbaldehyde, we obtained the new "stepped-parallel" 12 ligand 12, albeit in only 17% yield (Scheme 3).…”

Section: Scheme 3 Preparations Of Ligands 10 and 12mentioning

confidence: 99%

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Syntheses of new binucleating heterocyclic ligands

Slater¹,

Steel²

2006

Tetrahedron Letters

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Section: Bsupporting

confidence: 67%

Section: Scheme 3 Preparations Of Ligands 10 and 12mentioning

confidence: 99%

Syntheses of new binucleating heterocyclic ligands

Slater¹,

Steel²

2006

Tetrahedron Letters

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“…The controlled assembly of multinuclear metal complexes incorporating electrochemically and photochemically active moieties is of great interest for the fundamental understanding of energy and electron transfer − on a molecular level and the modeling of natural photosynthesis as well as for the design of molecular wires , and switches, , photocatalysts, − and information storage devices . (Polypyridine)ruthenium(II) complexes, especially the archetype compound [Ru(bpy) 3 ] 2+ (bpy = 2,2′-bipyridine), have found wide application in such arrays due to their high stability and outstanding photochemical properties.…”

Section: Introductionmentioning

confidence: 99%

Dual Emission and Excited-State Mixed-Valence in a Quasi-Symmetric Dinuclear Ru–Ru Complex

et al. 2014

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The synthesis and characterization of the new dinuclear dipeptide [(EtOOC-tpy)Ru(tpy-NHCO-tpy)Ru(tpy-NHCOCH3)](4+) 3(4+) of the bis(terpyridine)ruthenium amino acid [(HOOC-tpy)Ru(tpy-NH2)](2+) 1(2+) are described, and the properties of the dipeptide are compared to those of the mononuclear complex [(EtOOC-tpy)Ru(tpy-NHCOCH3)](2+) 4(2+) carrying the same functional groups. 3(4+) is designed to serve a high electronic similarity of the two ruthenium sites despite the intrinsic asymmetry arising from the amide bridge. This is confirmed via UV-vis absorption and NMR spectroscopy as well as cyclic voltammetry. 4(2+) and 3(4+) are emissive at room temperature, as expected. Moreover, 3(4+) exhibits dual emission from two different triplet states with different energies and lifetimes at room temperature. This is ascribed to the presence of a unique thermal equilibrium between coexisting [Ru(II)(tpy-NHCO-tpy(·-))Ru(III)] and [Ru(III)(tpy-NHCO-tpy(·-))Ru(II)] states leading to an unprecedented excited-state Ru(II)Ru(III) mixed-valent system via the radical anion bridge tpy-NHCO-tpy(·-). The mixed-valent cation 3(5+), on the other hand, shows no measurable interaction of the Ru(II)Ru(III) centers via the neutral bridge tpy-NHCO-tpy (Robin-Day class I). Reduction of 3(4+) to the radical cation 3(3+) by decamethylcobaltocene is bridge-centered as evidenced by rapid-freeze electron paramagnetic resonance spectroscopy. Interestingly, all attempts to observe 3(3+) via NMR and UV-vis absorption spectroscopy only led to the detection of the diamagnetic complex 3-H(3+) in which the bridging amide is deprotonated. Hence 3-H(3+) (and 4-H(+)) appear to reduce protons to dihydrogen. The ease of single and double deprotonation of 4(2+) and 3(4+) to 4-H(+), 3-H(3+), and 3-2H(2+) was demonstrated using a strong base and was studied using NMR and UV-vis absorption spectroscopies. The equilibrating excited triplet states of 3(4+) are reductively quenched by N,N-dimethylaniline assisted by hydrogen bonding to the bridging amide.

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“…Rigorous examination and consideration of the nomenclature challenges inherent in these situations has been limited, and the development and codification of required nomenclature has also lagged. As a consequence, ad hoc and mutually inconsistent approaches have been developed by individual research groups to address their particular needs [ 115 , 116 , 117 , 118 , 119 , 120 , 121 , 122 , 123 ]. It is clear that these situations are certainly not adequately covered in the standard recommendations from IUPAC [ 20 , 124 ].…”

Section: Complexes Of 11′-biisoquinolinesmentioning

confidence: 99%

1,1′-Biisoquinolines—Neglected Ligands in the Heterocyclic Diimine Family That Provoke Stereochemical Reflections

2021

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1,1′-Biisoquinolines are a class of bidentate nitrogen donor ligands in the heterocyclic diimine family. This review briefly discusses their properties and the key synthetic pathways available and then concentrates upon their coordination behaviour. The ligands are of interest as they exhibit the phenomenon of atropisomerism (hindered rotation about the C1–C1′ bond). A notation for depicting the stereochemistry in coordination compounds containing multiple stereogenic centers is developed. The consequences of the chirality within the ligand on the coordination behaviour is discussed in detail.

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Metal–metal interactions in dinuclear ruthenium complexes incorporating “stepped-parallel” bridging ligands: synthesis, stereochemistry and intervalence charge transfer

Cited by 22 publications

References 47 publications

Syntheses of new binucleating heterocyclic ligands

Syntheses of new binucleating heterocyclic ligands

Dual Emission and Excited-State Mixed-Valence in a Quasi-Symmetric Dinuclear Ru–Ru Complex

1,1′-Biisoquinolines—Neglected Ligands in the Heterocyclic Diimine Family That Provoke Stereochemical Reflections

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