Ruthenium(II) complexes of modified 1,10-phenanthrolines. 1. Synthesis and properties of complexes containing dipyridophenazines and a dicyanomethylene-substituted 1,10-phenanthroline

Ackermann, Martin N.; Interrante, L. V.

doi:10.1021/ic00192a014

Cited by 84 publications

(54 citation statements)

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“…[64,65] In addition, in order to visually understand the related properties of the Ru complex, the stereocontour graphs of some related frontier molecular orbitals of the Ru II complexes for S 0 in aqueous solution were drawn with Gaussview based on the computational results. [66] Materials cis-[Ru(bpy) 2 Cl 2 ]Á2H 2 O [67] and 1,10-phenanthroline-5,6dione [68] were synthesized according to the literature methods.…”

Section: Discussionmentioning

confidence: 99%

Synthesis, and Acid–Base and DNA-Binding Properties of a Thiophen-Appended Ruthenium Complex

et al. 2011

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2-(5-Phenylthiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (Hptip) and its Ru II complex [Ru(bpy) 2 (Hptip)](PF 6 ) 2 (where bpy ¼ 2,2 0 -bipyridine) have been synthesized and characterized by elemental analysis, 1 H NMR spectroscopy, and mass spectrometry. The acid-base properties of the complex were studied by UV-visible and luminescence spectrophotometric pH titrations, and ground-and excited-state acidity ionization constants were derived. The DNAbinding properties of [Ru(bpy) 2 (Hptip)](PF 6 ) 2 were also investigated by means of UV-vis and emission spectroscopy, salt effects, steady-state emission quenching by [Fe(CN) 6 ] 4À , DNA competitive binding with ethidium bromide, DNA melting experiments, and viscosity measurements. Density functional theoretical calculations were also carried out in order to understand the DNA binding properties.

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Section: Discussionmentioning

confidence: 99%

Synthesis, and Acid–Base and DNA-Binding Properties of a Thiophen-Appended Ruthenium Complex

et al. 2011

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“…The electrochemical behaviour of [Ru(bpy) 2 -(DPSalH 2 )] 2 + conforms to that of a [Ru(bpy) 3 ] 2 + -type complex ( Figure 5 ) and, as expected for a heteroleptic complex, the reduction pattern gives a clear indication of the energy levels of the p* orbitals of the ligands in the coordination sphere of Ru II . [10,18] is the irreversible character and the shift to more positive potential of the first reduction wave. This implies the presence of DPSalH 2 in the coordination sphere of ruthenium and that the addition of the first electron more likely occurs on the coordinated DPSalH 2 due to its more electron accepting character than bpy because of the two imino groups.…”

Section: Full Papermentioning

confidence: 99%

Heteroditopic Ligand Accommodating a Fused Phenanthroline and a Schiff Base Cavity as Molecular Spacer in the Study of Electron and Energy Transfer

Pellegrin

Quaranta

Dorlet

et al. 2005

Chemistry A European J

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The synthesis and characterisation of the heteroditopic ligand N,N'-bis(3,5-di-tert-butylsalicylidene)-5,6-(1,10-phenanthroline)diamine (DPSalH(2)) bearing a phenanthroline and a bis(salicylidene)diimine cavity are reported. This versatile ligand combines two of the most widely used ligands in coordination chemistry. Sequential metallation of the phenanthroline end with Ru(II) and the salophenic cavity with Cu(II) is described. Electrochemical behaviour of the supramolecular complexes [Ru(bpy)(2)(DPSalH(2))](2+) and [Ru(bpy)(2)(DPSalCu)](2+) are analysed in connection with UV/Vis and EPR spectroscopy. The data for the one-electron-reduced species and the singly oxidised species of the binuclear Ru(II)-Cu(II) complex confirmed the formation of metalloradical complexes. Density functional calculations on the free ligand and the copper-only complex indicate in both cases that the HOMOs and LUMOs are developed on the Schiff base cavity with minor contributions on the bipyridine end. These findings support a bichromophoric character for our ruthenium complexes in the ground state, a necessary condition in the design of supramolecular systems for the study of electron transfer. Photophysical studies indicate fast quenching of the triplet excited state in both complexes, which suggests strong intercomponent excited-state interactions. Evidence is presented that this quenching is due to intramolecular electron transfer, at least in the case of [Ru(bpy)(2)(DPSalH(2))](2+), for which a charge-separated state with a remarkable lifetime of about 30 mus was observed.

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“…However, this is only true if the processes of reduction and oxidation are as in Equations 1 and 2, respectively. [31] […”

Section: Complexesmentioning

confidence: 99%

A Rigid Molecular Scaffold Affixing a (Polypyridine)ruthenium(II)‐ and a Nickel(II)‐Containing Complex: Spectroscopic Evidence for a Weakly Coupled Bichromophoric System

et al. 2003

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The synthesis of DppztBuSalH2 (7), a rigid conjugated ditopic ligand containing a Dppz (dipyrido[3,2‐a:2′,3′‐c]phenazine) skeleton and a salophen‐type chelate, is reported. The complexes DppztBuSalNi (10), [Ru(bpy)2(DppztBuSalH2)]2+ (11), and [Ru(bpy)2(DppztBuSalNi)]2+ (12) have been prepared and characterised using common spectroscopic methods. Electrochemical, UV/Vis spectroelectrochemical and EPR studies were conducted on compounds 7, 10, 11, and 12. The singly reduced radical forms of 7 and 10 can be generated electrochemically, with the lone electron located on the low‐lying phenazine π*‐molecular orbital. Complexes 11 and 12 show several reduction waves and electronic and EPR data obtained for the electrogenerated singly reduced species show them to be closely related to the radical species 7·− and 10·−, respectively. The presence of nickel(II) in compound 12 renders the addition of the second electron on the phenazine group reversible. Both 11 and 12 show common features on the cathodic side of their cyclic voltammograms, with reversible one‐electron ruthenium‐centred oxidation. An additional low‐potential reversible‐oxidation wave is observed for 12, and this is ascribed to oxidation of the nickel(II) ion. The combined spectroscopic data best describe the ruthenium‐containing complexes as weakly coupled bichromophoric systems. Photophysical studies attest to the formation of a charge‐separated state for 11, whereas a strong quenching is detected for 12. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Ruthenium(II) complexes of modified 1,10-phenanthrolines. 1. Synthesis and properties of complexes containing dipyridophenazines and a dicyanomethylene-substituted 1,10-phenanthroline

Cited by 84 publications

References 0 publications

Synthesis, and Acid–Base and DNA-Binding Properties of a Thiophen-Appended Ruthenium Complex

Synthesis, and Acid–Base and DNA-Binding Properties of a Thiophen-Appended Ruthenium Complex

Heteroditopic Ligand Accommodating a Fused Phenanthroline and a Schiff Base Cavity as Molecular Spacer in the Study of Electron and Energy Transfer

A Rigid Molecular Scaffold Affixing a (Polypyridine)ruthenium(II)‐ and a Nickel(II)‐Containing Complex: Spectroscopic Evidence for a Weakly Coupled Bichromophoric System

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