Synthesis and spectroscopic and electrochemical properties of mononuclear and dinuclear bis(2,2'-bipyridyl)ruthenium complexes containing 3,5-bis(pyridin-2-yl)-1,2,4-triazole

Hage, Ronald; Dijkhuis, Anouk H. J.; Haasnoot, Jaap G.; Prins, R.; Reedijk, J.; Buchanan, Barbara E.; Vos, Johannes G.

doi:10.1021/ic00285a034

Cited by 123 publications

(83 citation statements)

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“…Two reversible oxidative processes are observed for each complex, both of which are assigned to one-electron metalcentered oxidations (Figure 8). The potential of the first oxidation step of the dinuclear complexe 1a is different than the value obtained for the related dinuclear compounds 13 [Ru(bpy) 2 (bpt)Ru(bpy) 2 ] 3+ (Table 1). For 1a (0.72 V vs SCE) the first oxidation is significantly less positive that for the related complex 13 [Ru(bpy) 2 (bpt)Ru(bpy) 2 ] 3+…”

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confidence: 58%

Excited State Localization and Internuclear Interactions in Asymmetric Ruthenium(II) and Osmium(II) bpy/tpy Based Dinuclear Compounds

et al. 2010

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Raman spectra. The interaction between the two metal centers, mediated by the bridging 1,2,4-triazolato moiety in the mixed valent state, is assigned as type II based on the observation of metal to metal charge transfer absorption bands at 7090 and 5990 cm -1 for 1a and 2a, respectively. The extent of localization of the emissive excited state was determined by transient resonance Raman and emission spectroscopy. Both 1a and 2a show phosphorescence at the same wavelengths; however, whereas for compound 1a the emission is based on the Ru(tpy)Cl-center, for 2a the emissive state is localized on the Os(bpy) 2 -unit. This indicates that also in the excited state there is efficient interaction between the two metal centers.

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confidence: 58%

Excited State Localization and Internuclear Interactions in Asymmetric Ruthenium(II) and Osmium(II) bpy/tpy Based Dinuclear Compounds

et al. 2010

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“…16 Analysis of the vis-NIR spectrum shows no evidence of an IT absorption band in the mixed valence state of complex 1 (see ESI). As for 1, oxidation of the dinuclear Os complex 2 leads to a decrease in the intensity of the MLCT absorption bands (see ESI) and 65 the simultaneous appearance of low intensity bands in the region 4450-5700 cm -1 assigned to osmium centred dp-dp transitions.…”

Section: Spectroelectrochemistrymentioning

confidence: 99%

“…Complexes 6 and 7 16 are bridged by the same bis-(pyridyltriazolato) ligand but differ in the metal centres (i.e. osmium vs. ruthenium).…”

Section: Comparison Of Pytpytr Bridged Complexes 6 Andmentioning

confidence: 99%

“…13 Amongst the many multinuclear polypyridyl complexes reported, 14 an interesting subclass is represented by those binuclear systems that display additional spectroelectrochemical features 15 due to the electronic interaction between the two metal centres in the mixed valence redox state(s). 15, 16 "Communication" between metal centres where direct overlap of atomic orbitals is not possible is achieved when the bridging ligand (BL) has a system of polarisable electrons that are capable of mediating 20 the redistribution of the electronic charge between the two metal centres. 17, 18 If the BL is sufficiently capable of mediating an internuclear interaction then direct (optical) electron transfer is possible in the mixed valence state (i.e., M II 1 M III 2 → M III 1 M II 2 ) 19, 20 and is manifested in the appearance of metal-to-25 metal (MM¢CT) or intervalence (IT) charge transfer 21-23 absorption bands, typically in the far red and near infrared.…”

Section: Introductionmentioning

confidence: 99%

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Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

et al. 2009

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A series of binuclear ruthenium and osmium complexes [(bipy) (5) and [(bipy) 2 Os(bpbt)Os(bipy) 2 ] 2+ (6) {bipy = 2,2¢-bipyridyl; qpy = 2,2¢:5¢,5¢¢:2¢¢,2¢¢¢-quaterpyridyl; pytr-bipy = 3-(2,2¢-bipyrid-6-yl)-5-(pyrid-2-yl)-1,2,4-triazolato, and bpbt = 5,5¢-bis-(pyrid-2¢¢-yl)-3,3¢-bis-1,2,4-triazolato} are reported. Analysis of the electrochemical data focuses on structural factors and on determining the extent of electronic communication between the metal centres in the mixed valence oxidation state. Intervalence charge transfer (IT) bands could be identified in the spectra of the complexes 4 and 6 only. Analysis of their spectroelectrochemical data leads to the conclusion that the IT is superexchange mediated through the HOMO of the bridging ligand. IntroductionMetal complexes based on polypyridyl ligands constitute versatile components for the construction of multifunctional supramolecular systems in molecular photonics and molecular electronics, 1 sensors, 2 photocatalysis, 3 solar energy 5 conversion, 4 artificial photosynthesis, 5 non-linear optics, 6 and electrochemoluminescence 7 amongst others. 8, 9 The myriad of applications are founded on the well defined chemistry of these compounds and take advantage of the versatile photophysical, 10 photochemical 11 and electrochemical 12 properties that are associ-10 ated with the metal-to-ligand charge-transfer (MLCT) excitation in these metal complexes. 13 Amongst the many multinuclear polypyridyl complexes reported, 14 an interesting subclass is represented by those binuclear systems that display additional spectroelectrochemical features 15 due to the electronic interaction between the two metal centres in the mixed valence redox state(s). 15,16 "Communication" between metal centres where direct overlap of atomic orbitals is not possible is achieved when the bridging ligand (BL) has a system of polarisable electrons that are capable of mediating 20 the redistribution of the electronic charge between the two metal centres. Sciences, Dublin City University, Dublin 9, Analysis of these absorption bands 25 can provide detailed information as to the nature and extent of the interaction between the metals centres. 30 Recently, we reported the synthesis and characterisation of a series of homo-and hetero-binuclear ruthenium(II) and osmium(II) complexes of the general formula [M 1 (bipy) 2 -BL-M 2 (bipy) 2 ], where M = Ru or Os, bipy is 2,2¢-bipyridyl (bipy), and BL the bridging ligands 2,2¢:5¢,5¢¢:2¢¢,2¢¢¢-quaterpyridyl (qpy), 3-(2,2¢-35 bipyrid-6-yl)-5-(pyrid-2-yl)-1,2,4-triazolato (pytr-bipy), and 5,5¢-bis-(pyrid-2¢¢-yl)-3,3¢-bis-1,2,4-triazolato (bpbt). 26 In the present contribution, we describe in detail the electrochemical and spectroelectrochemical properties of these compounds. The goal of the present study is to evaluate the extent 40 of electronic communication between the two metal centres as a function of the electronic properties of the bridging ligand and the positioning of the two metal centres. In particular, attention is directed towards the hom...

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“…1,4-Dihydroxybenzene (Aldrich) was purified by recrystallization from ethanol and Hbpt was prepared as reported in the literature (Hage et al, 1988). Co-crystals were obtained by refluxing Hbpt and hydroquinone in a 2:1 ratio in an ethanolwater solution.…”

Section: Methodsmentioning

confidence: 99%

A 2:1 Co-Crystal of Hydroquinone and 3,5-Bis(2-pyridyl)-1,2,4-triazole

Nieuwenhuyzen¹,

Keyes²,

Gallagher³

et al. 1997

Acta Crystallogr C

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Synthesis and spectroscopic and electrochemical properties of mononuclear and dinuclear bis(2,2'-bipyridyl)ruthenium complexes containing 3,5-bis(pyridin-2-yl)-1,2,4-triazole

Cited by 123 publications

References 9 publications

Excited State Localization and Internuclear Interactions in Asymmetric Ruthenium(II) and Osmium(II) bpy/tpy Based Dinuclear Compounds

Excited State Localization and Internuclear Interactions in Asymmetric Ruthenium(II) and Osmium(II) bpy/tpy Based Dinuclear Compounds

Spectroelectrochemical properties of homo- and heteroleptic ruthenium and osmium binuclear complexes: intercomponent communication as a function of energy differences between HOMO levels of bridge and metal centres

A 2:1 Co-Crystal of Hydroquinone and 3,5-Bis(2-pyridyl)-1,2,4-triazole

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