Comparison of the crystal structures of tris heterocyclic ligand complexes of ruthenium(II)

Rillema, D. Paul; Jones, Daniel S.; Woods, Clifton; Levy, H. A.

doi:10.1021/ic00039a049

Cited by 159 publications

(121 citation statements)

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“…The average Ru À N bond length is 2.058, 2.055 and 2.063 for I, II and III, respectively. These values fall within the same range as those found for [RuA C H T U N G T R E N N U N G (bpy) 3 ] 2 + (2.056 ) and related compounds [24] supporting the fact that the protonic states of the ligand do not influence the coordinating properties of the latter to the ruthenium(II) centre. The torsional angle between the imidazole and the phenyl ring is found to be around 17 and 148 for I and II, respectively while it is 38.58 for III.…”

Section: X-ray Structuressupporting

confidence: 81%

Influence of the Protonic State of an Imidazole‐Containing Ligand on the Electrochemical and Photophysical Properties of a Ruthenium(II)–Polypyridine‐Type Complex

Quaranta

Lachaud

Herrero

et al. 2007

Chemistry A European J

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The synthesis and characterisation of [Ru(bpy)2(PhenImHPh)]2+ where PhenImHPh represents the 2-(3,5-di-tert-butylphenyl)imidazo[4,5-f][1,10]phenanthroline ligand are described. The compounds issued from the three different protonic states of the imidazole ring [Ru(bpy)2(PhenImPh)]+ (I), [Ru(bpy)2(PhenImHPh)]2+ (II) and [Ru(bpy)2(PhenImH2Ph)]3+ (III) were isolated and spectroscopically characterised. The X-ray structures of [Ru(bpy)2(PhenImPh)](PF6)H2O.6 MeOH, [Ru(bpy)2(PhenImHPh)](NO3)2H2O.3 MeOH and [Ru(bpy)2(PhenImH2Ph)](PF6)3 5 H2O are reported. Electrochemical data obtained on these complexes indicate almost no potential shift for the Ru(III/II) redox couple. Therefore a Coulombic effect between the imidazole ring and the metal centre can be ruled out. The monooxidised forms of I and II have been characterised by EPR spectroscopy and are reminiscent of the presence of a radical species. The emission properties of the parent compound [Ru(bpy)2(PhenImHPh)]2+ were studied as a function of pH and both the lifetimes and intensities decreased upon deprotonation. Photophysical properties, investigated in the absence and presence of an electron acceptor (methylviologen), were distinctly different for the three compounds. Transient absorption features indicate that unique excited states are involved. Theoretical data obtained from DFT calculations in water on the three protonic forms are presented and discussed in the light of the experimental results.

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Section: X-ray Structuressupporting

confidence: 81%

Influence of the Protonic State of an Imidazole‐Containing Ligand on the Electrochemical and Photophysical Properties of a Ruthenium(II)–Polypyridine‐Type Complex

Quaranta

Lachaud

Herrero

et al. 2007

Chemistry A European J

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“…Selected distances and bond angles for 1. angles of 78.8(2)°, and the angles between the chelate rings are divided into the usual two groups of 85.9-88.5(2)°and 95.6-99.1(2)°( [15] and to bis(bipyridyl) complexes in general. [16,17] Similarly, the Ru-N bipyridyl bond lengths [2.050-2.078(4) Å] and the benzimidazole bond length [Ru-N(6) = 2.060(4) Å] are very similar to Ru-N bonds in the related complexes. [16,17] The N(6)-C (32) and N(6)-C(26) bond lengths of 1.399(6) and 1.335(5) Å are also similar to the previously reported Ru-benzimidazole complex [1.39(1) and 1.35(1) Å] as are the other N-C bonds within the bipyridyl rings.…”

Section: Resultsmentioning

confidence: 94%

Synthesis, Electrochemical and Electrogenerated Chemiluminescence Studies of Ruthenium(II) Bis(2,2′‐bipyridyl){2‐(4‐methylpyridin‐2‐yl)benzo[d]‐X‐azole} Complexes

et al. 2006

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A series of photoactive complexes of [Ru II bis(bipyridyl){2-(4-methylpyridin-2-yl)benzo[d]-X-azole}](PF 6 ) 2 (X = N-CH 3 , 1; S, 2; or O, 3) have been synthesized and fully characterized by proton and 13 C NMR spectroscopy and UV/Vis spectroscopy. The X-ray structure of 1 is also reported. The electrochemical behavior and the photophysical properties of 1-3 have been investigated. Cyclic voltammetry (CV) reveals the presence of three consecutive one-electron reduction processes and a single one-electron oxidation process that

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“…These Ru-N(bpy) bond distances are similar to those of PF6 salt (2.035(6) -2.074(6)Å, and av. 2.051 Å), 3 and [Ru(bpy)3](PF6)2 (2.056(2)Å), 6 and the remaining Ru1-N5 bond distance (2.0648(19)Å), which is between the Ru1 atom and the N5 atom of the pic ligand, is also similar to the corresponding distance in PF6 salt (2.068(5)Å). The Ru1-O1 bond distance (2.0872(15)Å) is close to that in PF6 salt (2.100(5)Å).…”

Section: Pf6mentioning

confidence: 57%

“…3,4 In the crystal structure, the dihedral angles between two pyridine rings within each 2,2′-bipyridyl ligand (10.3(3) and 14.4(2) ), are significantly larger than that in [Ru(bpy)3](PF6)2 (2.2(1) ). 6 Although a greater twisting of bpy ligands has not been noticed in the literature, 3 we take notice of the greater twisting and the hydrogen-bonding interactions between two oxygen atoms of a pic in a Ru(II) complex cation and 3,3′-protons of a bpy ligand in a neighboring complex cation; Fig. S1 in which the hydrogen-bonding diagram is drawn according to the CIF file of [Ru(pic)(bpy)2](PF6).…”

Section: Nn′)(dmso-s)2]mentioning

confidence: 99%

Crystal Structure of (2-Picolinato)bis(2,2′-bipyridine)ruthenium(II) Chloride

Toyama

Nakayasu

Nagao

2017

X-ray Structure Analysis Online

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11The coordination chemistry of ruthenium(II) complexes with polypyridyl ligands has been an area of great interest, because of their redox properties and photochemistry. 1 We reported on the syntheses, crystal structures, and isomerization reactions of the ruthenium(II) complexes bearing a di-2-pyridyl ketone (dpk); trans(Cl),cis(S)-[RuCl2(dpk-κ 2 N,O)(dmso-S)2] and cis(Cl),cis(S)-[RuCl2(dpk-κ2 The crystal structure of the trans(Cl),cis(S)-isomer revealed that the oxygen of the ketone group on the dpk ligand was able to act as an effective donor atom to from a N,O-coordination mode, which was kinetically more favorable than the N,N mode, but was thermodynamically unstable. In view of the hemilabile coordination ability of the N,O bidentate ligand, the 2-picolinic acid (Hpic) has great interest for us. One of the popular and typical Ru(II)N5O type complexes that includes a pic ligand is [Ru(pic)(bpy)2] + (bpy = 2,2′-bipyridine), which has been synthesized. [3][4][5] The crystal structure and 1 H NMR spectrum of [Ru(pic)(bpy)2](PF6) have been repotrted. 3,4 In the crystal structure, the dihedral angles between two pyridine rings within each 2,2′-bipyridyl ligand (10.3(3) and 14.4(2) ), are significantly larger than that in [Ru(bpy)3](PF6)2 (2.2(1) ). 6Although a greater twisting of bpy ligands has not been noticed in the literature, 3 we take notice of the greater twisting and the hydrogen-bonding interactions between two oxygen atoms of a pic in a Ru(II) complex cation and 3,3′-protons of a bpy ligand in a neighboring complex cation; Fig. S1 in which the hydrogen-bonding diagram is drawn according to the CIF file of [Ru(pic)(bpy)2](PF6). That is to say, the four O···H-C interactions between two Ru(II) complex cations allow the cations to come close to each other so that the bpy ligands are twisted. Similar O···H-C interactions between two O atoms of a ClO4 -ion and 3,3′-protons of a bpy ligand in {(μ-H2L)[Ru(bpy)2]2}(ClO4)2 (H4L = 1,5-diamino-9,10-anthraquinone) have also been observed, 7 in which the dihedral angles of the bpy ligands (9.9 and 10.4 ) are similar to those in [Ru(pic)(bpy)2](PF6). We thus feel a great interest in the structure of [Ru(pic)(bpy)2] + with another counter anion. Warren et al. isolated the Cl salt by converting it from PF6 salt using the ion-exchange resin. 5 We directly isolated a Ru(II) complex as Cl salt, [Ru(pic)(bpy)2]Cl, from the reaction mixture, and determined the crystal structure, as shown in Fig. 1 To the homogeneous dark-purple hydrolysis solution, a solution of Hpic (1.1 mmol) in ethanol (20 mL) was added, and the mixture was refluxed for 3 h. While refluxing, the solution turned from dark-purple to wine-red. The resulting wine-red solution was evaporated to dryness under a vacuum, and the residue was dissolved in 2 mL of water. An aqueous solution of HCl (1 M, 2 mL) was added to precipitate a brown-red solid.The brown-red solid, [Ru(pic)(bpy)2]Cl was collected by filtration, washed with a small amount of cold water, and dried in vacuo (0.93 mmol, 96%). The 1 H NMR spectr...

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Comparison of the crystal structures of tris heterocyclic ligand complexes of ruthenium(II)

Cited by 159 publications

References 0 publications

Influence of the Protonic State of an Imidazole‐Containing Ligand on the Electrochemical and Photophysical Properties of a Ruthenium(II)–Polypyridine‐Type Complex

Influence of the Protonic State of an Imidazole‐Containing Ligand on the Electrochemical and Photophysical Properties of a Ruthenium(II)–Polypyridine‐Type Complex

Synthesis, Electrochemical and Electrogenerated Chemiluminescence Studies of Ruthenium(II) Bis(2,2′‐bipyridyl){2‐(4‐methylpyridin‐2‐yl)benzo[d]‐X‐azole} Complexes

Crystal Structure of (2-Picolinato)bis(2,2′-bipyridine)ruthenium(II) Chloride

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