A strategy for improving the room-temperature luminescence properties of Ru(II) complexes with tridentate ligands

Several ruthenium(II) complexes with new tridentate polypyridine ligands have been prepared, and their photophysical properties have been studied. The new tridentate ligands are tpy-modified systems (tpy = 2,2':6',2' '-terpyridine) in which aromatic substituents designed to be coplanar with the tpy moiety are introduced, with the aim of enhancing delocalization in the acceptor ligand of the potentially luminescent metal-to-ligand charge-transfer (MLCT) state and increasing the MLCT-MC energy gap (MC = metal-centered excited state). Indeed, the Ru(II) complexes obtained with this new family of tridentate ligands exhibit long-lived luminescence at room temperature (up to 200 ns). The enhanced luminescence properties of these complexes support this design strategy and are superior to those of the model Ru(tpy)22+ compound and compare favorably with those of the best Ru(II) complexes with tridentate ligands reported so far.     

Photophysical and electrochemical properties of Ru(II) complexes containing tridentate bisphosphino-oligothiophene ligands

Nine Ru(II) complexes containing the conjugated oligothiophene ligands 3,3'-bis(diphenylphosphino)-2,2':5',2'-terthiophene (P(2)T(3)) and 4',3'-bis(diphenylphosphino)-3,3'-dihexyl- 2,2':5',2':5',2':5',2'-pentathiophene (P(2)T(5)) were prepared and characterized. P(2)T(3) and P(2)T(5) bond as tridentate ligands and three of the complexes (1, 2 and 5) form green five-coordinate Ru(II) complexes in solution. Cyclic voltammetry, variable temperature UV-vis spectroscopy and time-resolved transient absorption spectroscopy were used to characterize the electronic properties of the complexes. Increased conjugation in the complexes containing the P(2)T(5) ligand resulted in a lowering of the oxidation potential of the oligothiophene, but electropolymerization was not observed. The electronic spectra were dominated by π-π* transitions. All of the complexes were non-emissive both at room temperature and low temperature, indicating the excited state decays by other, non-radiative pathways. The transient absorption spectrum of complex 7 shows a species with a band at 475 nm and a lifetime of ～100 ns, assigned to a ligand-based triplet state.     

Ruthenium(II) complexes with improved photophysical properties based on planar 4'-(2-pyrimidinyl)-2,2':6',2' '-terpyridine ligands

A series of new tridentate polypyridine ligands, made of terpyridine chelating subunits connected to various substituted 2-pyrimidinyl groups, and their homoleptic and heteroleptic Ru(II) complexes have been prepared and characterized. The new metal complexes have general formulas [(R-pm-tpy)Ru(tpy)]2+ and [Ru(tpy-pm-R)2]2+ (tpy = 2,2':6',2' '-terpyridine; R-pm-tpy = 4'-(2-pyrimidinyl)-2,2':6',2' '-terpyridine with R = H, methyl, phenyl, perfluorophenyl, chloride, and cyanide). Two of the new metal complexes have also been characterized by X-ray analysis. In all the R-pm-tpy ligands, the pyrimidinyl and terpyridyl groups are coplanar, allowing an extended delocalization of acceptor orbital of the metal-to-ligand charge-transfer (MLCT) excited state. The absorption spectra, redox behavior, and luminescence properties of the new Ru(II) complexes have been investigated. In particular, the photophysical properties of these species are significantly better compared to those of [Ru(tpy)2]2+ and well comparable with those of the best emitters of Ru(II) polypyridine family containing tridentate ligands. Reasons for the improved photophysical properties lie at the same time in an enhanced MLCT-MC (MC = metal centered) energy gap and in a reduced difference between the minima of the excited and ground states potential energy surfaces. The enhanced MLCT-MC energy gap leads to diminished efficiency of the thermally activated pathway for the radiationless process, whereas the similarity in ground and excited-state geometries causes reduced Franck Condon factors for the direct radiationless decay from the MLCT state to the ground state of the new complexes in comparison with [Ru(tpy)2]2+ and similar species.     

Designing tridentate ligands for ruthenium(II) complexes with prolonged room temperature luminescence lifetimes

Coordination complexes have been used extensively as the photoactive component of artificial photosynthetic devices. While polynuclear arrays increase the probability of light absorption, the incorporation of the stereogenic Ru(2,2'-bipyridine)(3)(2+) motif gives rise to diastereomeric mixtures whereas the achiral Ru(2,2':6',2"-terpyridine)(2)(2+) motif creates stereopure polynuclear complexes. Thus, polynuclear arrays composed of ruthenium(II) complexes of tridentate ligands are the targets of choice for light-harvesting devices. As Ru(II) complexes of tridentate ligands have short excited state lifetimes at room temperature (r. t.), considerable effort has been focused on trying to increase their r. t. luminescence lifetime for practical applications. This tutorial review will report on the sophisticated synthetic strategies currently in use to enhance the room temperature photophysical properties of Ru(II) complexes of tridentate ligands.     

Fused donor-acceptor ligands in RuII chemistry: synthesis, electrochemistry and spectroscopy of [Ru(bpy)3-n(TTF-dppz)n](PF6)2.

Three ruthenium(II) polypyridine complexes of general formula [Ru(bpy)(3-n)(TTF-dppz)n](PF6)2 (n=1-3, bpy=2,2'-bipyridine), with one, two or three redox-active TTF-dppz (4',5'-bis(propylthio)tetrathiafulvenyl[i]dipyrido[3,2-a:2',3'-c]phenazine) ligands, were synthesised and fully characterised. Their electrochemical and photophysical properties are reported together with those of the reference compounds [Ru(bpy)3](PF6)2, [Ru(dppz)3](PF6)2 and [Ru(bpy)2(dppz)](PF6)2 and the free TTF-dppz ligand. All three complexes show intraligand charge-transfer (ILCT) fluorescence of the TTF-dppz ligand. Remarkably, the complex with n=1 exhibits luminescence from the Ru(2+)-->dppz metal-to-ligand charge-transfer ((3)MLCT) state, whereas for the other two complexes, a radiationless pathway via electron transfer from a second TTF-dppz ligand quenches the (3)MLCT luminescence. The TTF fragments as electron donors thus induce a ligand-to-ligand charge-separated (LLCS) state of the form TTF-dppz- -Ru(2+)-dppz-TTF(+). The lifetime of this LLCS state is approximately 2.3 micros, which is four orders of magnitude longer than that of 0.4 ns for the ILCT state, because recombination of charges on two different ligands is substantially slower.     

Role of electronic structure on DNA light-switch behavior of Ru(II) intercalators

A series of ruthenium(II) complexes possessing ligands with an extended pi system were synthesized and characterized. The complexes are derived from [Ru(bpy)3](2+) (1, bpy = 2,2'-bipyridine) and include [Ru(bpy)2(tpphz)](2+) (2, tpphz = tetrapyrido[3,2-a:2',3'-c:3',2'-h:2',3'-j]phenazine), [Ru(bpy)2(dppx)](2+) (3, dppx = 7,8-dimethyldipyrido[3,2-a:2',3'-c]phenazine), [Ru(bpy)2(dppm2)](2+) (4, dppm2 = 6-methyldipyrido[3,2-a:2',3'-c]phenazine), and [Ru(bpy)2(dppp2)](2+) (5, dppp2 = pyrido[2',3':5,6]pyrazino[2,3-f][1,10]phenanthroline). The excited-state properties of these complexes, including their DNA "light-switch" behavior, were compared to those of [Ru(bpy)2(dppz)](2+) (6, dppz = dipyrido[3,2-a:2',3'-c]phenazine). Whereas 2, 3, and 4 can be classified as DNA light-switch complexes, 5 exhibits negligible luminescence enhancement in the presence of DNA. Because relative viscosity experiments show that 2-6 bind to DNA by intercalation, their electronic absorption and emission spectra, electrochemistry, and temperature dependence of the luminescence were used to explain the observed differences. The small energy gap between the lowest-lying dark excited state and the bright state in 2-4 and 6 is related to the ability of these complexes to exhibit DNA light-switch behavior, whereas the large energy gap in 5 precludes the emission enhancement in the presence of DNA. The effect of the energy gap among low-lying states on the photophysical properties of 1-6 is discussed. In addition, DFT and TD-DFT calculations support the conclusions from the experiments.     

Water oxidation catalysis: influence of anionic ligands upon the redox properties and catalytic performance of mononuclear ruthenium complexes

Aiming at highly efficient molecular catalysts for water oxidation, a mononuclear ruthenium complex Ru(II)(hqc)(pic)(3) (1; H(2)hqc = 8-hydroxyquinoline-2-carboxylic acid and pic = 4-picoline) containing negatively charged carboxylate and phenolate donor groups has been designed and synthesized. As a comparison, two reference complexes, Ru(II)(pdc)(pic)(3) (2; H(2)pdc = 2,6-pyridine-dicarboxylic acid) and Ru(II)(tpy)(pic)(3) (3; tpy = 2,2':6',2"-terpyridine), have also been prepared. All three complexes are fully characterized by NMR, mass spectrometry (MS), and X-ray crystallography. Complex 1 showed a high efficiency toward catalytic water oxidation either driven by chemical oxidant (Ce(IV) in a pH 1 solution) with a initial turnover number of 0.32 s(-1), which is several orders of magnitude higher than that of related mononuclear ruthenium catalysts reported in the literature, or driven by visible light in a three-component system with [Ru(bpy)(3)](2+) types of photosensitizers. Electrospray ionization MS results revealed that at the Ru(III) state complex 1 undergoes ligand exchange of 4-picoline with water, forming the authentic water oxidation catalyst in situ. Density functional theory (DFT) was employed to explain how anionic ligands (hqc and pdc) facilitate the 4-picoline dissociation compared with a neutral ligand (tpy). Electrochemical measurements show that complex 1 has a much lower E(Ru(III)/Ru(II)) than that of reference complex 2 because of the introduction of a phenolate ligand. DFT was further used to study the influence of anionic ligands upon the redox properties of mononuclear aquaruthenium species, which are postulated to be involved in the catalysis cycle of water oxidation.     

Changing the role of 2,2'-bipyridine from secondary ligand to protagonist in [Ru(bpy)2(N-N)]2+ complexes: low-energy, red emission from a ruthenium(II)-to-2,2'-bipyridine 3MLCT state

Two new bidentate ligands (1 and 2) with bicyclic guanidine moieties were synthesized and attached to a Ru(II)(bpy)(2) core (bpy = 2,2'-bipyridine) to afford complexes 3 and 4, which were characterized by spectroscopic and electrochemical methods. Complex 4 was further characterized by X-ray crystallography. In cyclic voltammetric studies, both complexes show a Ru(II/III) couple, which is 500 mV less positive than the Ru(II/III) couple of Ru(bpy)(3)(2+). The (1)MLCT and (3)MLCT states of 3 (560 nm/745 nm) and 4 (550 nm/740 nm) are significantly red-shifted with respect to Ru(bpy)(3)(2+) (440 nm/620 nm). Compounds 3 and 4 exhibit emission from a Ru(II)-to-bpy (3)MLCT state, which is rarely the emitting state at λ > 700 nm in [Ru(bpy)(2)(N-N)](2+) complexes.     

Synthesis, luminescence, and electrochemical studies of tris(homoleptic) ruthenium(II) and osmium(II) complexes of 6'-tolyl-2,2':4',2'-terpyridine

The synthesis and photophysical and electrochemical properties of tris(homoleptic) complexes [Ru(tpbpy)3](PF6)2 (1) and [Os(tpbpy)3](PF6)2 (2) (tpbpy = 6'-tolyl-2,2':4',2' '-terpyridine) are reported. The ligand tpbpy is formed as the side product during the synthesis of 4'-tolyl-2,2':6',2' '-terpyridine (ttpy) and characterized by single-crystal X-ray diffraction: monoclinic, P21/c. The tridentate tpbpy coordinates as a bidentate ligand. The complexes 1 and 2 exhibit two intense absorption bands in the UV region (200-350 nm) assignable to the ligand-centered (1LC) pi-pi* transitions. The ruthenium(II) complex exhibits a broad absorption band at 470 nm while the osmium(II) complex exhibits an intense absorption band at 485 nm and a weak band at 659 nm assignable to the MLCT (dpi-pi*) transitions. A red shifting of the dpi-pi* MLCT transition is observed on going from the Ru(II) to the Os(II) complex as expected from the high-lying dpi Os orbitals. These complexes exhibit ligand-sensitized emission at 732 and 736 nm, respectively, upon light excitation onto their MLCT band through excitation of higher energy LC bands at room temperature. The MLCT transitions and the emission maxima of 1 and 2 are substantially red-shifted compared to that of [Ru(bpy)3](PF6)2 and [Os(bpy)3](PF6)2. The emission of both the complexes in the presence of acid is completely quenched indicating that the emission is not due to the protonation of the coordinated ligands. Our results indicate the occurrence of intramolecular energy transfer from the ligand to the metal center. Both the complexes undergo quasi-reversible metal-centered oxidation, and the E1/2 values for the M(II)/M(III) redox couples (0.94 and 0.50 V versus Ag/Ag+ for 1 and 2, respectively) are cathodically shifted with respect to that of [Ru(bpy)3](PF6)2 and [Os(bpy)3](PF6)2 (E1/2 = 1.28 and 1.09 V versus Ag/Ag+, respectively). The tris(homoleptic) Ru(II) and Os(II) complexes 1 and 2 could be used to construct polynuclear complexes by using the modular synthetic approach in coordination compounds by exploiting the coordinating ability of the pyridine substituent. Furthermore, these complexes offer the possibility of studying the influence of electron-withdrawing and electron-donating substituents on the photophysical properties of Ru(II) and Os(II) polypyridine complexes.     

Valence and spin situations in isomeric [(bpy)Ru(Q')2]n (Q' = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine). An experimental and DFT analysis

The article deals with the ruthenium complexes, [(bpy)Ru(Q')(2)] (1-3) incorporating two unsymmetrical redox-noninnocent iminoquinone moieties [bpy = 2,2'-bipyridine; Q' = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, aryl = C(6)H(5) (Q'(1)), 1; m-Cl(2)C(6)H(3) (Q'(2)), 2; m-(OCH(3))(2)C(6)H(3) (Q'(3)), 3]. 1 and 3 have been preferentially stabilised in the cc-isomeric form while both the ct- and cc-isomeric forms of 2 are isolated [ct: cis and trans and cc: cis and cis with respect to the mutual orientations of O and N donors of two Q']. The isomeric identities of 1-3 have been authenticated by their single-crystal X-ray structures. The collective consideration of crystallographic and DFT data along with other analytical events reveals that 1-3 exhibit the valence configuration of [(bpy)Ru(II)(Q'(Sq))(2)]. The magnetization studies reveal a ferromagnetic response at 300 K and virtual diamagnetic behaviour at 2 K. DFT calculations on representative 2a and 2b predict that the excited triplet (S = 1) state is lying close to the singlet (S = 0) ground state with singlet-triplet separation of 0.038 eV and 0.075 eV, respectively. In corroboration with the paramagnetic features the complexes exhibit free radical EPR signals with g～2 and (1)HNMR spectra with broad aromatic proton signals associated with the Q' at 300 K. Experimental results in conjunction with the DFT (for representative 2a and 2b) reveal iminoquinone based preferential electron-transfer processes leaving the ruthenium(ii) ion mostly as a redox insensitive entity: [(bpy)Ru(II)(Q'(Q))(2)](2+) (1(2+)-3(2+)) ? [(bpy)Ru(II)(Q(')(Sq))(Q(')(Q))](+) (1(+)-3(+)) ? [(bpy)Ru(II)(Q(')(Sq))(2)] (1-3) ? [(bpy)Ru(II)(Q(')(Sq))(Q(')(Cat))](-)/[(bpy)Ru(III)(Q(')(Cat))(2)](-) (1(-)-3(-)). The diamagnetic doubly oxidised state, [(bpy)Ru(II)(Q'(Q))(2)](2+) in 1(2+)-3(2+) has been authenticated further by the crystal structure determination of the representative [(bpy)Ru(II)(Q'(3))(2)](ClO(4))(2) [3](ClO(4))(2) as well as by its sharp (1)H NMR spectrum. The key electronic transitions in each redox state of 1(n)-3(n) have been assigned by TD-DFT calculations on representative 2a and 2b.     

Synthesis, structure and spectral and redox properties of new mixed ligand monomeric and dimeric Ru(II) complexes: predominant formation of the "cis-alpha" diastereoisomer and unusual 3MC emission by dimeric complexes

The tetradentate ligands 1,8-bis(pyrid-2-yl)-3,6-dithiaoctane (pdto) and 1,8-bis(benzimidazol-2-yl)-3,6-dithiaoctane (bbdo) form the complexes [Ru(pdto)(mu-Cl)](2)(ClO(4))(2) 1 and [Ru(bbdo)(mu-Cl)](2)(ClO(4))(2) 2 respectively. The new di-mu-chloro dimers 1 and 2 undergo facile symmetrical bridge cleavage reactions with the diimine ligands 2,2'-bipyridine (bpy) and dipyridylamine (dpa) to form the six-coordinate complexes [Ru(pdto)(bpy)](ClO(4))(2) 3, [Ru(bbdo)(bpy)](ClO(4))(2) 4, [Ru(pdto)(dpa)](ClO(4))(2) 5 and [Ru(bbdo)(dpa)](ClO(4))(2) 6 and with the triimine ligand 2,2':6,2'-terpyridine (terpy) to form the unusual seven-coordinate complexes [Ru(pdto)(terpy)](ClO(4))(2) 7 and [Ru(bbdo)(terpy)](ClO(4))(2) 8. In 1 the dimeric cation [Ru(pdto)(mu-Cl)](2)(2+) is made up of two approximately octahedrally coordinated Ru(II) centers bridged by two chloride ions, which constitute a common edge between the two Ru(II) octahedra. Each ruthenium is coordinated also to two pyridine nitrogen and two thioether sulfur atoms of the tetradentate ligand. The ligand pdto is folded around Ru(II) as a result of the cis-dichloro coordination, which corresponds to a "cis-alpha" configuration [DeltaDelta/LambdaLambda(rac) diastereoisomer] supporting the possibility of some attractive pi-stacking interactions between the parallel py rings at each ruthenium atom. The ruthenium atom in the complex cations 3a and 4 exhibit a distorted octahedral coordination geometry composed of two nitrogen atoms of the bpy and the two thioether sulfur and two py/bzim nitrogen atoms of the pdto/bbdo ligand, which is actually folded around Ru(II) to give a "cis-alpha" isomer. The molecule of complex 5 contains a six-coordinated ruthenium atom chelated by pdto and dpa ligands in the expected distorted octahedral fashion. The (1)H and (13)C NMR spectral data of the complexes throw light on the nature of metal-ligand bonding and the conformations of the chelate rings, which indicates that the dithioether ligands maintain their tendency to fold themselves even in solution. The bis-mu-chloro dimers 1 and 2 show a spin-allowed but Laporte-forbidden t(2g)(6)((1)A(1g))--> t(2g)(5) e(g)(1)((1)T(1g), (1)T(2g)) d-d transition. They also display an intense Ru(II) dpi--> py/bzim (pi*) metal-to-ligand charge transfer (MLCT) transition. The mononuclear complexes 3-8 exhibit dpi-->pi* MLCT transitions in the range 340-450 nm. The binuclear complexes 1 and 2 exhibit a ligand field ((3)MC) luminescence even at room temperature, whereas the mononuclear complexes 3 and 4 show a ligand based radical anion ((3)MLCT) luminescence. The binuclear complexes 1 and 2 undergo two successive oxidation processes corresponding to successive Ru(II)/Ru(III) couples, affording a stable mixed-valence Ru(II)Ru(III) state (K(c): 1, 3.97 x 10(6); 2, 1.10 x 10(6)). The mononuclear complexes 3-7 exhibit only one while 8 shows two quasi-reversible metal-based oxidative processes. The coordinated 'soft' thioether raises the redox potentials significantly by stabilising the 'soft' Ru(II) oxidation state. One or two ligand-based reduction processes were also observed for the mononuclear complexes.     

Synthesis, structure, redox properties, and catalytic activity of new ruthenium complexes containing neutral or anionic and facial or meridional ligands: an evaluation of electronic and geometrical effects

The synthesis of a family of new Ru complexes containing meridional or facial tridentate ligands with the general formula [Ru(II)(T)(D)(X)](n+) [T = 2,2':6',2' '-terpyridine or tripyrazolylmethane; D = 4,4'-dibenzyl-4,4',5,5'-tetrahydro-2,2'-bioxazole (S,S-box-C) or 2-[((1'S)-1'-(hydroxymethyl)-2'-phenyl)ethylcarboxamide]-(4S)-4-benzyl-4,5-dihydrooxazole (S,S-box-O); X = Cl, H(2)O, MeCN or pyridine] has been described. All complexes have been spectroscopically characterized in solution through (1)H NMR and UV-vis techniques. Furthermore, all of the chloro complexes presented here have also been characterized in the solid state through monocrystal X-ray diffraction analysis. The oxazolinic S,S-box-C ligands undergo a Ru-assisted hydrolysis reaction generating the corresponding amidate anionic oxazolinic ligands S,S-box-O, which are also strongly attached to the metal center and produce a strong sigma-donation effect over the Ru metal center. The redox properties of all complexes have also been studied by means of cyclic voltammetry, strongly reflecting the nature of the ligands; both effects, geometrical (facial vs meridional) and electronic (neutral vs anionic), can be unveiled and rationalized. Finally, the reactivity of the Ru-OH(2) complexes has been tested with regard to the epoxidation of trans-stilbene, and it has been shown that, in this particular case, the reactivity is practically not dependent on the redox potentials of the catalyst but, in sharp contrast, it is strongly dependent on the geometry of the tridentate ligands.     

Wirelike dinuclear ruthenium complexes connected by bis(ethynyl)oligothiophene

Preparation and characterization of a series of rodlike binuclear ruthenium polyynediyl complexes capped with redox-active organometallic fragments [(bph)(PPh3)2Ru]+ (bph=N-(benzoyl)-N'-(picolinylidene)-hydrazine) or [(Phtpy)(PPh3)2Ru]2+ (Phtpy=4'-phenyl-2,2':6',2' '-terpyridine) have been carried out. The length of the molecular rods is extended by successive insertion of 2,5-thiophene or 1,4-phenylene spacers in the bridging ligands. Oxidation of thiophene-containing Ru2II,II complexes induces isolation of stable Ru2II,III or Ru2III,III species. Electrochemical and UV-vis-NIR spectral studies demonstrate that the polyynediyl bridges with 2,5-thiophene units are more favorable for metal-metal charge transfer compared with those containing the same number of 1,4-phenylene units. Successive increase of thiophene spacers in mixed-valence complexes {RuII}-CC(C4H2S)mCC-{RuIII} (m=1, 2, 3) induced a smooth transition from almost electronic delocalization (m=1) to localization (m=3). For binuclear ruthenium complexes with intramolecular electron transfer transmitted across nine Ru-C and C-C bonds, electronic conveying capability follows {Ru}-CC(CC)2CC-{Ru}>{Ru}-CC(C4H2S)CC-{Ru}>{Ru}-CC(C6H4)CC-{Ru}>{Ru}-CC(CH=CH)2CC-{Ru}. It is revealed that molecular wires capped with electron-rich (bph)(PPh3)2Ru endgroups are much more favorable for electronic communication than the corresponding electron-deficient (Phtpy)(PPh3)2Ru-containing counterparts. The intermetallic electronic communication is fine-tuned by modification of both the bridging spacers and the ancillary ligands.     

Rapid energy transfer in bichromophoric tris-bipyridyl/cyclometallated ruthenium(II) complexes

The synthesis, characterization, and photophysical properties of the N6-N5C bichromophoric [(bpy)2Ru(I)Ru(ttpy)][PF6]3 (bpy is 2,2'-bipyridine and ttpy is 4'-p-tolyl-2,2':6',2'-terpyridine) and [(bpy)2Ru(II)Ru(ttpy)][PF6]3 (I and II are bpy-dipyridylbenzene ditopic ligands bridged by an ethynyl and phenyl unit, respectively) complexes are reported together with the model mononuclear complexes [(bpy)2Ru(I)][PF6]2, [(bpy)2Ru(II)][PF6]2, [Ru(VI)(ttpy)][PF6] (VI is 3,5-di(2-pyridyl)-biphenyl) and [Ru(dpb)(ttpy)][PF(6)] (Hdpb is 1,3-di(2-pyridyl)-benzene). The electrochemical data show that there is little ground state electronic communication between the metal centers in the bimetallic complexes. Selective excitation of the N(5)C unit in the bichromophoric systems leads to luminescence typical for a bis-tridentate cyclometallated ruthenium complex and is similar to the [Ru(VI)(ttpy)][PF6] model complex. In contrast, the luminescence from the tris-bidentate N6 unit is efficiently quenched by energy transfer to the N5C unit. The energy transfer rate has been determined by femtosecond pump-probe measurements to 0.7 ps in the ethynyl-linked [(bpy)2Ru(I)Ru(ttpy)][PF6]3 and to 1.5 ps in the phenyl-linked [(bpy)2Ru(II)Ru(ttpy)][PF6]3 (in acetonitrile solution at 298 K), and is inferred to occur via a Dexter mechanism.     

Ruthenium complexes of easily accessible tridentate ligands based on the 2-aryl-4,6-bis(2-pyridyl)-s-triazine motif: absorption spectra, luminescence properties, and redox behavior

A family of tridendate ligands 1 a-e, based on the 2-aryl-4,6-di(2-pyridyl)-s-triazine motif, was prepared along with their hetero- and homoleptic Ru(II) complexes 2 a-e ([Ru(tpy)(1 a-e)](2+); tpy=2,2':6',2"-terpyridine) and 3 a-e ([(Ru(1 a-e)(2)](2+)), respectively. The ligands and their complexes were characterized by (1)H NMR spectroscopy, ES-MS, and elemental analysis. Single-crystal X-ray analysis of 2 a and 2 e demonstrated that the triazine core is nearly coplanar with the non-coordinating ring, with dihedral angles of 1.2 and 18.6 degrees, respectively. The redox behavior and electronic absorption and luminescence properties (both at room temperature in liquid acetonitrile and at 77 K in butyronitrile rigid matrix) were investigated. Each species undergoes one oxidation process centered on the metal ion, and several (three for 2 a-e and four for 3 a-e) reduction processes centered on the ligand orbitals. All compounds exhibit intense absorption bands in the UV region, assigned to spin-allowed ligand-centered (LC) transitions, and moderately intense spin-allowed metal-to-ligand charge-transfer (MLCT) absorption bands in the visible region. The compounds exhibit relatively intense emissions, originating from triplet MLCT levels, both at 77 K and at room temperature. The incorporation of triazine rings and the near planarity of the noncoordinating ring increase the luminescence lifetimes of the complexes by lowering the energy of the (3)MLCT state and creating a large energy gap to the dd state.     

1,10]-Phenanthrolin-2-yl ketones and their coordination chemistry

A synthetic protocol involving the Friedl?nder reaction of 8-amino-7-quinolinecarbaldehyde followed by potassium dichromate oxidation was applied to 2,3,4-pentanetrione-3-oxime and 1-(pyrid-2'-yl)propane-1,2-dione-1-oxime to provide the ligands di-(phenathrolin-2-yl)-methanone (1) and phenanthrolin-2-yl-pyrid-2-yl-methanone (8), respectively. Ligand 1 complexed as a planar tetradentate with Pd(II) to form [Pd(1)](BF4)2 and with Ru(II) and two 4-substituted pyridines (4-R-py) to form [Ru(1)(4-R-py)2](PF6)2 where R = CF3, CH3, and Me2N. With [Ru(bpy)2Cl2], the dinuclear complex [(bpy)2Ru(1)Ru(bpy)2](PF6)4 was formed (bpy = 2,2'-bipyridine). Ligand 8 afforded the homoleptic Ru(II) complex [Ru(8)2](PF6)2, as well as the heteroleptic complex [Ru(8)(tpy)](PF6)2 (tpy = 2,2';6,2'-terpyridine). The ligands and complexes were characterized by their NMR and IR spectra, as well as an X-ray structure determination of [Ru(1)(4-CH3-py)2](PF6)2. Electrochemical analysis indicated metal-based oxidation and ligand-based reduction that was consistent with results from electronic absorption spectra. The complexes [Ru(1)(4-R-py)2](PF6)2 were sensitive to the 4-substituent on the axial pyridine: electron donor groups facilitated the oxidation while electron-withdrawing groups impeded it.     

Luminescent bis-tridentate ruthenium(II) and osmium(II) complexes based on terpyridyl-imidazole ligand: synthesis, structural characterization, photophysical, electrochemical, and solvent dependence studies

Homo- and heteroleptic bis-tridentate ruthenium(II) and osmium(II) complexes of compositions [(tpy-PhCH(3))Ru(tpy-HImzPh(3))](ClO(4))(2) (1), [(H(2)pbbzim)Ru(tpy-HImzPh(3))] (ClO(4))(2) (2) and [M(tpy-HImzPh(3))(2)](ClO(4))(2) [M = Ru(II) (3) and Os(II) (4)], where tpy-PhCH(3) = p-methylphenyl terpyridine, H(2)pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine and tpy-HImzPh(3) = 4'-[4-(4,5-diphenyl-1H-imidazol-2-yl)-phenyl]-[2,2':6',2']terpyridine, have been synthesized and characterized by using standard analytical and spectroscopic techniques. These compounds were designed to increase the room temperature excited-state lifetimes of bisterpyridine-type ruthenium(II) and osmium(II) complexes. The X-ray crystal structures of two homoleptic complexes 3 and 4 have been determined and show that both the compounds crystallized in orthorhombic form with space group Fddd. The photophysical and redox properties of the complexes have been thoroughly investigated. All the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 6-35 ns. The complexes are found to undergo one reversible oxidation in the positive potential window (0 to +1.6 V) and one irreversible and two successive quasi-reversible reductions in the negative potential window (0 to -2.0 V). The influence of solvents on the photophysical properties of the complexes has also been investigated in detail.     

Photophysical properties of ruthenium(II) polyazaaromatic compounds: a theoretical insight

Quantum-chemical methods are applied to study the nature of the excited states relevant in the photophysical processes (absorption and emission) of a series of polyazaaromatic-ligand-based ruthenium(II) complexes. The electronic and optical properties of the free polyazaaromatic ligands and their corresponding ruthenium(II) complexes are determined on the basis of correlated Hartree-Fock semiempirical approaches. While the emission of complexes containing small-size ligands, such as 1,10-phenanthroline or 2,2'-bipyridine, arises from a manifold of metal-to-ligand charge-transfer triplet states ((3)MLCTs), an additional ligand-centered triplet state ((3)L) is identified in the triplet manifold of complexes containing a pi-extended ligand such as dipyrido[3,2-a:2',3'-c]phenazine, tetrapyrido[3,2-a:2',3'-c:3',2'-h:2',3'-j]phenazine, and 1,10-phenanthrolino[5,6-b]-1,4,5,8,9,12-hexaazatriphenylene. Recent experimental data are interpreted in light of these theoretical results; namely, the origin for the abnormal solvent- and temperature-dependent emission measured in pi-extended Ru complexes is revisited.     

The multichromophore approach: prolonged room-temperature luminescence lifetimes in Ru(II) complexes based on tridentate polypyridine ligands

A new family of ruthenium(II) complexes with multichromophoric properties was prepared based on a "chemistry-on-the-complex" synthetic approach. The new compounds are based on tridentate chelating sites (tpy-type ligands, tpy=2,2':6',2'-terpyridine) and most of them carry appended anthryl chromophores. Complexes 2 a and 2 b were synthesized through the Pd-catalyzed Suzuki coupling reaction between 9-anthrylboronic acid and the chloro ligands on the presursor species 1 a and 1 b, respectively. The monocoupling product 2 c was also synthesized as the starting complex for a dimetallic complex under optimized Suzuki coupling conditions. The palladium(0)-catalyzed homocoupling reaction on complexes 1 a and 2 c led to dimetallic Ru(II) species 2 d and 2 e, respectively. The solid structures of complexes 2 a and 2 b were characterized by X-ray diffraction. The absorption spectra, redox behavior, luminescence properties (both at room temperature and at 77 K), and transient absorption spectra and decays of 2 a-e were investigated. The absorption spectra of all new species are dominated by ligand-centered (LC) bands in the UV region and metal-to-ligand charge-transfer (MLCT) bands in the visible region. The new compounds undergo reversible metal-centered oxidation processes and several ligand-centered reduction processes, which have been assigned to specific sites. The complexes exhibit luminescence both at room temperature in fluid solution and at 77 K in rigid matrices; the emission was attributed to (3)MLCT states at room temperature and to the lowest-lying anthracene triplet ((3)An) at low temperature, except for 2 c, which does not contain any anthryl chromophore and whose low temperature emission is also of MLCT origin. The luminescence lifetimes of complexes 2 a-d showed that multichromophoric behavior occurs in these species, allowing the luminescence lifetime of the Ru(II)-based chromophores to be prolonged to the microsecond timescale, with the anthryl groups behaving as energy-storage elements for the repopulation of the (3)MLCT state. Nanosecond transient-absorption spectroscopy confirmed the equilibration process between the triplet MLCT and An levels at room temperature. Thermodynamic and kinetic factors governing the equilibration time and the lifetime of the equilibrated excited state are discussed.     

New members of the [Ru(diimine)(CN)(4)](2-) family: structural, electrochemical and photophysical properties

A series of complexes of the type K(2)[Ru(NN)(CN)(4)] has been prepared, in which NN is a diimine ligand, and were investigated for both their structural and photophysical properties. The ligands used (and the abbreviations for the resulting complexes) are 3-(2-pyridyl)pyrazole (Ru-pypz), 2,2'-bipyrimidine (Ru-bpym), 5,5'-dimethyl-2,2'-bipyridine (Ru-dmb), 1-ethyl-2-(2-pyridyl)benzimidazole (Ru-pbe), bidentate 2,2':6',2'-terpyridine (Ru-tpy). The known complexes with = 2,2'-bipyridine (Ru-bpy) and 1,10-phenathroline (Ru-phen) were also included in this work. A series of crystallographic studies showed that the [Ru(NN)(CN)(4)](2-) complex anions form a range of elaborate coordination networks when crystallised with either K(+) or Ln(3+) cations. The K(+) salts are characterised by a combination of near-linear Ru-CN-K bridges, with the cyanides coordinating to K(+) in the usual 'end-on' mode, and unusual side-on pi-type coordination of cyanide ligands to K(+) ions. With Ln(3+) cations in contrast only Ru-CN-Ln near-linear bridges occurred, affording 1-dimensional helical or diamondoid chains, and 2-dimensional sheets constituted from linked metallamacrocyclic rings. All of the K(2)[Ru(CN)(4)] complexes show a reversible Ru(II)/Ru(III) couple (ca.+0.9 V vs. Ag/AgCl in water), the exception being Ru-tpy whose oxidation is completely irreversible. Luminescence studies in water showed the presence of (3)MLCT-based emission in all cases apart from Ru-bpym with lifetimes of tens/hundreds of nanoseconds. Time-resolved infrared studies showed that in the (3)MLCT excited state the principal C-N stretching vibration shifts to positive energy by ca. 50 cm(-1) as a consequence of the transient oxidation of the metal centre to Ru(III) and the reduction in back-bonding to the cyanide ligands; measurement of transient decay rates allowed measurements of (3)MLCT lifetimes for those complexes which could not be characterised by luminescence spectroscopy. A few complexes were also examined in different solvents (MeCN, dmf) and showed much weaker emission and shorter excited-state lifetimes in these solvents compared to water.