Luminescence of Eu3+ and Tb3+ Complexes of Two Macrobicyclic Ligands Derived from a Tetralactam Ring and a Chromophoric Antenna

Two macrobicyclic ligands derived from an 18‐membered tetralactam ring and 2,2′‐bipyridine or 2,6‐bis(pyrazol‐1‐yl)pyridine moieties, 1 and 2 , respectively, form stable complexes with Gd^III, Eu^III, and Tb^III ions in aqueous solution. The ligand‐based luminescence is retained in the Gd^III cryptates, whereas this radiative deactivation is quenched in the Eu^III and Tb^III cryptates by ligand‐to‐metal energy transfer, resulting in the usual metal‐centered emission spectra. Singlet‐ and triplet‐state energies, emission‐decay lifetimes, and luminescence yields were measured. [Tb⊂ 1 ]³⁺ cryptate shows a long luminescence lifetime (τ=1.12 ms) and a very high metal luminescence quantum yield (Φ=0.25) in comparison with those reported in the literature for Tb³⁺ complexes sensitized by a bipyridine chromophore. By comparison to [Ln⊂ 1 ]³⁺, [Ln⊂ 2 ]³⁺ presents markedly lower luminescence properties, due to worse interaction between the 2,6‐bis(pyrazol‐1‐yl)pyridine unit and the metal ion. Moreover, the luminescent metal and the triplet ligand energy levels of [Eu⊂ 2 ]³⁺ do not match. The effects of H₂O molecules coordinated to the metal centre and of thermally activated decay processes on nonradiative deactivation to the ground‐state are also reported.     

Metal‐Ion Sensing Europium(III) Complexes with Bidentate Phosphine Oxide Ligands Containing a 2,2′‐Bipyridine Framework

Novel Eu^III complexes with bidentate phosphine oxide ligands containing a bipyridine framework, i.e., [3,3′‐bis(diphenylphosphoryl)‐2,2′‐bipyridine]tris(hexafluoroacetylacetonato)europium(III) ([Eu(hfa)₃(BIPYPO)]) and [3,3′‐bis(diphenylphosphoryl)‐6,6′‐dimethyl‐2,2′‐bipyridine]tris(hexafluoroacetylacetonato)europium(III) ([Eu(hfa)₃(Me‐BIPYPO)]), were synthesized for lanthanide‐based sensor materials having high emission quantum yields and effective chemosensing properties. The emission quantum yields of [Eu(hfa)₃(BIPYPO)] and [Eu(hfa)₃(Me‐BIPYPO)] were 71 and 73%, respectively. Metal‐ion sensing properties of the Eu^III complexes were also studied by measuring the emission spectra of Eu^III complexes in the presence of Zn^II or Cu^II ions. The metal‐ion sensing and the photophysical properties of luminescent Eu^III complexes with a bidentate phosphine oxide containing 2,2′‐bipyridine framework are demonstrated for the first time.     

Synthesis and Properties of Sodium and Europium(III) Cryptates Incorporating the 2,2′-Bipyridine 1,1′-Dioxide and 3,3′-Biisoquinoline 2,2′-Dioxide Units

The sodium and europium cryptates of the new macrobicyclic ligands 2 and 3 incorporating the 2,2′-bipyri dine 1,1′-dioxide and 3,3′-biisoquinoline 2,2′-dioxide units, respectively, have been prepared. The Eu^III complexes present characteristic ¹H-NMR spectra, showing large shifts, and are strongly luminescent in aqueous solution. These markedly improved luminescent properties, compared to the europium cryptate of the parent macrobicyclic ligand 1 , may be ascribed at least in part to a better shielding of the bound cation by the N-oxide sites.     

Synthesis and Properties of Macrobicyclic Cryptates Incorporating Five- and Six-Membered Biheteroaryl Units

The socium cryptates of the macrobicyclic ligands 1–6 have been synthesized by direct macrobicyclisation or by stepwise procedures. They incorporate 2,2′-bithiazole, 2,2′-biimidazole, 2.2′-bipyrimidine as well as 2,2′-bipyridine units. Treatment of the sodium complexes with europium(III) chloride gave the corresponding Eu^III cryptates. The structural and spectral properties of these compounds are described. The Eu^III complexes present characteristic ¹H-NMR chemical-shift features. Their luminescence properties are described.     

New 2,2′-Bipyridine Derivatives and Their Luminescence Properties with Europium(III) and Terbium(III) Ions

Twenty differently substituted 2,2′,2″,2? -[(2,2′-bipyridine-6,6′-diyl)bis(methylenenitrilo)]tetrakis(acetc acids) 75–94 were synthesized with the purpose of developing new markers to be used in bioaffinity assays based on the unique luminescence properties of Eu^III and Tb^III ions. The relative luminescence yields, excitation maxima, and emission decay constants were determined for the corresponding Eu^III and Tb^III chelates. The substituents at the bipyridine moiety had a significant effect on the luminescence properties: the best relative luminescence yields R were obtained for ligands with electron-donating substituents (e.g. Me, Ph), electron-withdrawing substituents (e.g. NO₂, COOH) had a reverse effect. However, no clear correlation between the relative luminescence yields and the substituent parameters was found.     

Influence of Chelating Groups on the Luminescence Properties of Europium(III) and Terbium(III) chelates in the 2,2′-bipyridine series

Eight different 2,2′-bipyridine derivatives, i.e. 2, 5, 8, 10, 12, 13, 15 , and 19 (Schemes 1 and 2), were prepared to study the influence of the chelating groups on the luminescence properties of their Eu^III and Tb^III chelates. According to our luminescence results, 2,2′-(methylenenitrilo)bis(acetic acid) as well as (methylenenitrilo)bis-(methylphosphonic acid) in 6- and 6′-position of 2,2′-bipyridine is a suitable group when developing luminescent markers for bioaffinity assays based on time-resolved luminescence measurement.     

Localization of electronic excitation energy in Ru(2,2′-bipyridine)2(2,2′-bipyridine-4,4′-dicarboxylic acid)2+ and related complexes

The absorption spectra of Ru(2,2′-bipyridine)₂ (2,2′-bipyridine-4,4′-dicarboxylic acid)²⁺ (I) and its diethyl ester (II) are closely related and are both significantly different from the spectra of the mono-protonated (Ia) and deprotonated (Ib) complexes. Luminescence polarization measurements show that for I and II the luminescent states have the transferred electron in the bipy-4,4′(COOH)₂ and bipy-4,4′(COOEt)₂ ligands, respectively, rather than in the unsubstituted bipy ligands.     

Crystal Structures of the Lanthanum(III), Europium(III), and Terbium(III) Cryptates of Tris(bipyridine) Macrobicyclic Ligands

The crystal structures of the La^III, Eu^III, and Tb^III complexes of macrobicyclic [bpy.bpy.bpy] ligands, [La³⁺ ? 1 ]3 Cl^? ( = 3- La), [Tb³⁺ ? 1 ]3 Cl^? ( = 3- Tb), and [Eu³⁺ ? 2 ]3 C1^? ( = 3- Eu), have been determined. They confirm the cryptate nature of these species, the cations being bound to the eight N-sites of the ligand. The macrobicycle presents two open faces, thus allowing additional coordination of two species, Cl^? ions or H₂O molecules, to the bound cations. These data provide structural support for the photophysical studies of the luminescent properties of the Eu^III and Tb^III cryptates, which indicated residual coordination of H₂O molecules.     

Synthesis and crystal structures of mononuclear iridium (III) acetylacetonate complexes bearing an axial bipyridine ligand

Three new iridium (III) acetylacetonate complexes with an axial bipyridine ligand were synthesised via the direct reaction of [bis(acac-O,O′)(acac-C³)Ir(H₂O)] and the corresponding bipyridine, and their molecular structures were determined by using single-crystal X-ray diffraction. The bipyridine used was di-2-pyridylketone, 2,2′-bipyridine and 2,2′-bipyridylamine, respectively. The results revealed that only mononuclear iridium complexes were obtained, although bipyridine has two N coordinate atoms, probably due to the great steric hindrance existing around the coordinate sphere if two bis(acac-O,O′)(acac-C³)Ir units were bridged by bipyridine. All these complexes are coordinated in one axial direction by bipyridine as a mono-dentate ligand in a slightly distorted octahedral coordination geometry.     

Three Novel Mixed‐ligand Cadmium(II) Sulfonates with Aza‐aromatic Skeltons as Co‐ligands

To survey the influence of aza‐aromatic co‐ligands on the structure of Cadmium(II) sulfonates, three Cd(II) complexes with mixed‐ligand, [Cd^II(ANS)₂(phen)₂] ( 1 ), [Cd^II(ANS)₂(2,2′‐bipy)₂] ( 2 ) and [Cd^II(ANS)₂(4,4′‐bipy)₂]_n ( 3 ) (ANS = 2‐aminonaphthalene‐1‐sulfonate; phen = 1,10‐phenanthroline; 2,2′‐bipy = 2,2′‐bipyridine; 4,4′‐bipy = 4,4′‐bipyridine) were synthesized by hydrothermal methods and structurally characterized by elemental analyses, IR spectra, and single crystal X‐ray diffraction. Of the three complexes, ANS consistently coordinates to Cd²⁺ ion as a monodentate ligand. While phen in 1 and 2,2′‐bipy in 2 act as N,N‐bidentate chelating ligands, leading to the formation of a discrete mononuclear unit; 4,4′‐bipy in 3 bridges two Cd^II atoms in bis‐monodentate fashion to produce a 2‐D layered network, suggesting that the conjugate skeleton and the binding site of the co‐ligands have a moderate effect on molecular structure, crystal stacking pattern, and intramolecular weak interactions. In addition, the three complexes exhibit similar luminescent emissions originate from the transitions between the energy levels of sulfonate anions.     

Synthesis and photophysical properties of novel amphiphilic ruthenium (II) complexes containing 4,4′‐dialkylaminomethyl‐2,2′‐bipyridyl ligands

The synthesis of a number of new 2,2′‐bipyridine ligands functionalized with bulky amino side groups is reported. Three homoleptic polypyridyl ruthenium (II) complexes, [Ru(L)₃]²⁺ 2(PF₆^?), where L is 4,4′‐dioctylaminomethyl‐2,2′‐bipyridine (Ru4a), 4,4′‐didodecylaminomethyl‐2,2′‐bipyridine (Ru4b) and 4,4′‐dioctadodecylaminomethyl‐2,2′‐bipyridine (Ru4c), have been synthesized. These compounds were characterized and their photophysical properties examined. The electronic spectra of three complexes show pyridyl π → π* transitions in the UV region and metal‐to‐ligand charge transfer bands in the visible region. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and Properties of Acyclic and Cryptate Europium(III) Complexes Incorporating the 3,3′-Biisoquinoline 2,2′-Dioxide Unit

The lithium and europium(III) cryptates of a macrobicyclic ligand 1 incorporating the 3,3′-biisoquinoline 2,2′-dioxide 2 have been prepared. The Eu(III) complex [Eu(2)₂]Cl₃ has also been obtained. These Eu(III) complexes present characteristic ¹H-NMR spectra containing markedly shifted resonances. They are strongly luminescent; the emission spectra, quantum yields, and lifetimes have been determined.     

Interligand energy transfer in europium(III) mesogenic adducts

An analysis of the absorption and luminescence spectra and luminescence kinetics showed that in the Eu(DK)₃bpy_17-17 mesogenic adduct, 5,5′-diheptadecyl-2,2′-bipyridine (bpy_17-17) took an active part in the energy transfer to the Eu³⁺ ion. The interligand energy transfer from β-diketonate (DK) ligands was the major mechanism of excitation of bpy_17-17. Importantly, the interligand excitation complex considerably decreased radiation losses during the energy transfer from the absorbing DK ligands to the emitting level of Eu³⁺.     

Molecular wiring of LiMnPO4 (olivine) by ruthenium(II)-bipyridine complexes

LiMnPO₄ (olivine) was surface-modified by two different complexes: Ru-bis(4,4′-diethoxycarbonyl-2,2′-bipyridine)(4,4′-dicarboxylate-2,2′-bipyridine) and Ru-bis(4-carboxylic acid-4′-carboxylate-2,2′-bipyridine)(4,4′-dinonyl-2,2′bipyridine). These complexes have redox potentials of 4.45 and 4.25 V vs. Li/Li⁺, respectively, and are both active for molecular wiring of LiMnPO₄. The surface-confined Ru(II)/Ru(III) redox reaction propagates across the monolayer via hole-hopping, allowing a subsequent chemical delithiation of the underneath olivine towards MnPO₄. The activity of LiMnPO₄ is about half of that of LiFePO₄ (olivine) at similar experimental conditions.     

A series of new oxo-vanadium(IV) complexes with octahedral coordinated vanadium centers

A series of new oxo-vanadium(IV) complexes, [VOCl0.69(OH)0.31 (2,2′-bipy)2]Cl·2H2O (1, 2,2′-bipy?=?2,2′-bipyridine) [(VO)₂Cl₄(4,4'-bipy)₃ (H₂O)₂] (2, 4,4'-bipy?=?4,4'-bipyridine), [VO(ida)(H₂O)]_n (3, H₂ida?=?iminodiacetic acid), and [(VO)₂(oa)₄]_n·4n(H₃O)·n(H₂O) (4, H₂oa?=?oxalic acid), have been synthesized and structurally characterized. 1 contains a [VOCl_0.69(OH)_0.31(2,2′-bipy)₂]⁺ cation, Cl ^– anion and two free H₂O molecules. 2 exhibits a binuclear centrosymmetric moiety built up from two [VOCl₂(4,4'-bipy)(H₂O)] units and one bridging 4,4'-bipy ligand, which provides a rare example of a 4,4'-bipy molecule acting as monodentate ligand. 3 displays a neutral chain [VO(ida)(H₂O)]_n constructed by the linkages of [VO(H₂O)]²⁺ units and ida^2? bridging ligands, while 4 offers the only example of three kinds of oa^2- ligands coexisting within the same anionic chain [(VO)₂(oa)₄^4-]_n. Their spectroscopic properties were investigated, and the magnetic susceptibility of 4 shows antiferromagnetic behavior.     

Photosensitized Generation of Singlet Oxygen from (Substituted Bipyridine)ruthenium(II) Complexes

Photophysical properties in dilute MeCN solution are reported for seven Ru^II complexes containing two 2,2′‐bipyridine (bpy) ligands and different third ligands, six of which contain a variety of 4,4′‐carboxamide‐disubstituted 2,2′‐bipyridines, for one complex containing no 2,2′‐bipyridine, but 2 of these different ligands, for three multinuclear Ru^II complexes containing 2 or 4 [Ru(bpy)₂] moieties and also coordinated via 4,4′‐carboxamide‐disubstituted 2,2′‐bipyridine ligands, and for the complex [(Ru(bpy)₂(L)]²⁺ where L is N,N′‐([2,2′‐bipyridine]‐4,4′‐diyl)bis[3‐methoxypropanamide]. Absorption maxima are red‐shifted with respect to [Ru(bpy)₃]²⁺, as are phosphorescence maxima which vary from 622 to 656 nm. The lifetimes of the lowest excited triplet metal‐to‐ligand charge transfer states ³MLCT in de‐aerated MeCN are equal to or longer than for [Ru(bpy)₃]²⁺ and vary considerably, i.e., from 0.86 to 1.71 μs. Rate constants k_q for quenching by O₂ of the ³MLCT states were measured and found to be well below diffusion‐controlled, ranging from 1.2 to 2.0⋅10⁹ dm³ mol⁻¹ s⁻¹. The efficiencies f of singlet‐oxygen formation during oxygen quenching of these ³MLCT states are relatively high, namely 0.53 – 0.89. The product of k_q and f gives the net rate constant k for quenching due to energy transfer to produce singlet oxygen, and k_q−k equals k, the net rate constant for quenching due to energy dissipation of the excited ³MLCT states without energy transfer. The quenching rate constants were both found to correlate with ΔG^CT, the free‐energy change for charge transfer from the excited Ru complex to oxygen, and the relative and absolute values of these rate constants are discussed.     

Luminescence Properties of Eu3+ Complexes of Tripode and Tetrapode Ligands Containing 2,2′-Bipyridine Units

The Eu³⁺ complexes of the tripode and tetrapode ligands 1 and 2 , respectively, containing 2,2′-bipyridine coordinating units have been prepared. The UV absorption and luminescence spectra, lifetimes, and quantum yields have been measured under a variety of experimental conditions. The contributions of different paths to the decay of the luminescent excited state are evaluated, and the structures of the complexes are discussed on the basis of spectroscopic and photophysical data.     

Shielding of Electron Acceptors Coordinated to Rhenium(I) by Carboxylato Groups. Intraligand and Charge‐Transfer Excited‐State Properties of fac‐(‘Anthraquinone‐2‐carboxylato')(2,2′‐bipyridine)tricarbonylrhenium (fac‐[ReI(aq‐2‐CO2)(2,2′‐bipy)(CO)3])

The photophysical and photochemical properties of (OC‐6‐33)‐(2,2′‐bipyridine‐κN¹,κN¹′)tricarbonyl(9,10‐dihydro‐9,10‐dioxoanthracene‐2‐carboxylato‐κO)rhenium (fac‐[Re^I(aq‐2‐CO₂)(2,2′‐bipy)(CO)₃]) were investigated and compared to those of the free ligand 9,10‐dihydro‐9,10‐dioxoanthracene‐2‐carboxylate (=anthraquinone‐2‐carboxylate) and other carboxylato complexes containing the (2,2′‐bipyridine)tricarbonylrhenium ([Re(2,2′‐bipy)(CO)₃]) moiety. Flash and steady‐state irradiations of the anthraquinone‐derived ligand (λ_exc 337 or 351 nm) and of its complex reveal that the photophysics of the latter is dominated by processes initiated in the Re‐to‐(2,2′‐bipyridine) charge‐transfer excited state and 2,2′‐bipyridine‐ and (anthraquinone‐2‐carboxylato)‐centered intraligand excited states. In the reductive quenching by N,N‐diethylethanamine (TEA) or 2,2′,2″‐nitrilotris[ethanol] TEOA, the reactive states are the 2,2′‐bipyridine‐centered and/or the charge‐transfer excited states. The species with a reduced anthraquinone moiety is formed by the following intramolecular electron transfer, after the redox quenching of the excited state: [Re^I(aq−2−CO₂)(2,2′‐bipy^.)(CO)₃]⁻⇌[Re^I(aq−2−CO₂^.)(2,2′‐bipy)(CO)₃]⁻ The photophysics, particularly the absence of a Re^I‐to‐anthraquinone charge‐transfer excited state photochemistry, is discussed in terms of the electrochemical and photochemical results.     

Metallomacrocycles with a Difference: Macrocyclic Complexes with Exocyclic Ruthenium(II)‐Containing Domains

The templated synthesis of organic macrocycles containing rings of up to 96 atoms and three 2,2′‐bipyridine (bpy) units is described. Starting with the bpy‐centred ligands 5,5′‐bis[3‐(1,4‐dioxahept‐6‐enylphenyl)]‐2,2′‐bipyridine and 5,5′‐bis[3‐(1,4,7‐trioxadec‐9‐enylphenyl)]‐2,2′‐bipyridine, we have applied Grubbs’ methodology to couple the terminal alkene units of the coordinated ligands in [FeL₃]²⁺ complexes. Hydrogenation and demetallation of the iron(II)‐containing macrocyclic complexes results in the isolation of large organic macrocycles. The latter bind {Ru(bpy)₂} units to give macrocyclic complexes with exocyclic ruthenium(II)‐containing domains. The complex [Ru(bpy)₂(L)]²⁺ (isolated as the hexafluorophosphate salt), in which L=5,5′‐bis[3‐(1,4,7,10‐tetraoxatridec‐12‐enylphenyl)]‐2,2′‐bipyridine, undergoes intramolecular ring‐closing metathesis to yield a macrocycle which retains the exocyclic {Ru(bpy)₂} unit. The poly(ethyleneoxy) domains in the latter macrocycle readily scavenge sodium ions, as proven by single‐crystal X‐ray diffraction and atomic absorption spectroscopy data for the bulk sample. In addition to the new compounds, a series of model complexes have been fully characterized, and representative single‐crystal X‐ray structural data are presented for iron(II) and ruthenium(II) acyclic and macrocyclic species.     

A surface enhanced Raman study of the adsorption of tris(2,2-bipyridine)ruthenium(II) and substituted analogues on chemically-deposited silver films

The surface enhanced resonance Raman spectroscopy (SERRS) of a series of tris(2,2′-bipyridine)ruthenium(II) complexes on chemically produced silver films is reported. The SERR spectra of [Ru(bipy)₃]²⁺, several tris complexes of Ru(II) containing substituted 2,2′-bipyridine (4,4′-dimethyl-,4,4′diphenyl-, 4,4′-diamino- and 4,4′-diethylcarboxylate-2,2′-bipyridine) ligands and the neutral cis-bis complexes [Ru(bipy)₂(NCS)₂] and [Ru(bipy)₂Cl₂] show very high band intensities. The large enhancement arises from the combination of the inherent resonance Raman effect and the surface plasmon resonance (due to the rough nature of the silver film). The molecules are not chemisorbed on the silver surface and hence the enhancement occurs solely via the electromagnetic mechanism. Ale SERR spectra are virtually free of the fluorescence which dominates the corresponding RR spectra thus illustrating the use of SERRS in the vibrational spectroscopy of strongly luminescing species. The SERRS spectra of the substituted 2,2′-bipyridine complexes are discussed.