Synthesis and characterization of tris(heteroleptic) Ru(II) complexes bearing styryl subunits

We have developed and optimized a well-controlled and refined methodology for the synthesis of substituted π-conjugated 4,4'-styryl-2,2'-bipyridine ligands and also adapted the tris(heteroleptic) synthetic approach developed by Mann and co-workers to produce two new representative Ru(II)-based complexes bearing the metal oxide surface-anchoring precursor 4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine. The two targeted Ru(II) complexes, (4,4'-dimethyl-2,2'-bipyridine)(4,4'-di-tert-butyl-2,2'-bipyridine)(4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine) ruthenium(II) hexafluorophosphate, [Ru(dmbpy)(dtbbpy)(p-COOMe-styryl-bpy)](PF(6))(2) (1) and (4,4'-dimethyl-2,2'-bipyridine)(4,4'-dinonyl-2,2'-bipyridine)(4,4'-bis[E-(p-methylcarboxy-styryl)]-2,2'-bipyridine) ruthenium(II) hexafluorophosphate, [Ru(dmbpy)(dnbpy)(p-COOMe-styryl-bpy)](PF(6))(2) (2) were obtained as analytically pure compounds in high overall yields (>50% after 5 steps) and were isolated without significant purification effort. In these tris(heteroleptic) molecules, NMR-based structural characterization became nontrivial as the coordinated ligand sets each sense profoundly distinct magnetic environments greatly complicating traditional 1D spectra. However, rational two-dimensional approaches based on both homo- and heteronuclear couplings were readily applied to these structures producing quite definitive analytical characterization and the associated methodology is described in detail. Preliminary photoluminescence and photochemical characterization of 1 and 2 strongly suggests that both molecules are energetically and kinetically suitable to serve as sensitizers in energy-relevant applications.     

Electron-rich heteroaromatic conjugated bipyridine based ruthenium sensitizer for efficient dye-sensitized solar cells

A novel heteroleptic ruthenium complex carrying a heteroaromatic-4,4'-pi-conjugated 2,2'-bipyridine [Ru(II)LL'(NCS)(2)] (L = 4,4'-bis[(E)-2-(3,4-ethylenedioxythien-2-yl)vinyl]-2,2'-bipyridine, L' = 4,4'-(dicarboxylic acid)-2,2'-bipyridine) was synthesized and used in dye-sensitized solar cells, yielding photovoltaic efficiencies of 9.1% under standard global AM 1.5 sunlight.     

New luminescent cyclometalated iridium(III) diimine complexes as biological labeling reagents

We report the synthesis, characterization, and photophysical and electrochemical properties of thirty luminescent cyclometalated iridium(III) diimine complexes [Ir(N-C)(2)(N-N)](PF(6)) (HN-C = 2-phenylpyridine, Hppy; 2-(4-methylphenyl)pyridine, Hmppy; 3-methyl-1-phenylpyrazole, Hmppz; 7,8-benzoquinoline, Hbzq; 2-phenylquinoline, Hpq; N-N = 4-amino-2,2'-bipyridine, bpy-NH(2); 4-isothiocyanato-2,2'-bipyridine, bpy-ITC; 4-iodoacetamido-2,2'-bipyridine, bpy-IAA; 5-amino-1,10-phenanthroline, phen-NH(2); 5-isothiocyanato-1,10-phenanthroline, phen-ITC; 5-iodoacetamido-1,10-phenanthroline, phen-IAA). The X-ray crystal structure of [Ir(mppz)(2)(bpy-NH(2))](PF(6)) has also been investigated. Upon irradiation, all the complexes display intense and long-lived luminescence under ambient conditions and in 77-K glass. On the basis of the photophysical and electrochemical data, the emission of most of these complexes is assigned to an excited state of predominantly triplet metal-to-ligand charge-transfer ((3)MLCT) (dpi(Ir) --> pi(N-N)) character. In some cases, triplet intraligand ((3)IL) (pi --> pi)(N-N or N-C(-)) excited states have also been identified. In view of the specific reactivity of the isothiocyanate and iodoacetamide moieties toward the primary amine and sulfhydryl groups, respectively, we have labeled various biological molecules with a selection of these luminescent iridium(III) complexes. The photophysical properties of the luminescent conjugates have been investigated. In addition, a heterogeneous assay for digoxin has also been designed on the basis of the recognition of biotinylated anti-digoxin by avidin labeled with one of the luminescent iridium(III) complexes.     

Mono- and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes

We report the synthesis of free 1,6,7,12-tetraazaperylene (tape). Tape was obtained from 1,1'-bis-2,7-naphthyridine by potassium promoted cyclization followed by oxidation with air. Mono- and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes of the general formulas [Ru(L-L)(2)(tape)](PF(6))(2), [1](PF(6))(2)-[5](PF(6))(2), and [{Ru(L-L)(2)}(2)(μ-tape)](PF(6))(4), [6](PF(6))(4)-[10](PF(6))(4), with{L-L = phen, bpy, dmbpy (4,4'-dimethyl-2,2'-bipyridine), dtbbpy (4,4'-ditertbutyl-2,2'-bipyridine) and tmbpy (4,4'5,5'-tetramethyl-2,2'-bipyridine)}, respectively, were synthesized. The X-ray structures of tape·2CHCl(3) and the mononuclear complexes [Ru(bpy)(2)(tape)](PF(6))(2)·0.5CH(3)CN·0.5toluene, [Ru(dmbpy)(2)(tape)](PF(6))(2)·2toluene and [Ru(dtbbpy)(2)(tape)](PF(6))(2)·3acetone·0.5H(2)O were solved. The UV-vis absorption spectra and the electrochemical behavior of the ruthenium(ii) tape complexes were explored and compared with the data of the analogous dibenzoeilatin (dbneil), 2,2'-bipyrimidine (bpym) and tetrapyrido[3,2-a:2',3'-c:3',2'-h:2',3'-j]phenazin (tpphz) species.     

Light-emitting electrochemical cells based on a supramolecularly-caged phenanthroline-based iridium complex

The complex [Ir(ppy)(2)(pphen)][PF(6)] (Hppy = 2-phenylpyridine, pphen = 2-phenyl-1,10-phenanthroline) has been prepared and evaluated as an electroluminescent component for light-emitting electrochemical cells (LECs). Like in analogous LECs using bpy-based iridium(III) complexes a significant enhancement of the device stability is observed.     

Amphiphilic ruthenium sensitizers and their applications in dye-sensitized solar cells

Amphiphilic ligands 4,4'-bis(1-adamantyl-aminocarbonyl)-2,2'-bipyridine (L(1)), 4,4'-bis[5-[N-[2-(3beta-cholest-5-en-3-ylcarbamate-N-yl)ethyl]aminocarbonyl]]-2,2'-bipyridine (L(2)), 4,4'-bis[5-[N-[2-(3beta-cholest-5-en-3-ylcarbamate-N-yl)propyl]aminocarbonyl]]-2,2'-bipyridine (L(3)), and 4,4'-bis(dodecan-12-ol)-2,2'-bipyridine (L(4)) and their heteroleptic ruthenium(II) complexes of the type [Ru(II)LL(1)(NCS)(2)] (5), [Ru(II)LL(2)(NCS)(2)] (6), [Ru(II)LL(3)(NCS)(2)] (7), and [Ru(II)LL(4)(NCS)(2)] (8) (where L = 4,4'-bis(carboxylic acid)-2,2'-bipyridine) have been synthesized starting from dichloro(p-cymene)ruthenium(II) dimer. All the ligands and the complexes were characterized by analytical, spectroscopic, and electrochemical techniques. The performance of these complexes as charge-transfer photosensitizers in nanocrystalline TiO(2)-based solar cells was studied. When complexes 5-8 anchored onto a 12 + 4 microm thick nanocrystalline TiO(2) films, very efficient sensitization was achieved (85 +/- 5% incident photon-to-current efficiencies in the visible region, using an electrolyte consisting of 0.6 M butylmethylimidazolium iodide, 0.05 M I(2), 0.1 M LiI, and 0.5 M tert-butyl pyridine in 1:1 acetonitrile + valeronitrile). Under standard AM 1.5 sunlight, the complex 8 yielded a short-circuit photocurrent density of 17 +/- 0.5 mA/cm(2), the open-circuit voltage was 720 +/- 50 mV, and the fill factor was 0.72 +/- 0.05, corresponding to an overall conversion efficiency of 8.8 +/- 0.5%.     

Synthesis, characterisation and application of iridium(III) photosensitisers for catalytic water reduction

The synthesis of novel, monocationic iridium(III) photosensitisers (Ir-PSs) with the general formula [Ir(III)(C^N)(2)(N^N)](+) (C^N: cyclometallating phenylpyridine ligand, N^N: neutral bidentate ligand) is described. The structures obtained were examined by cyclic voltammetry, UV/Vis and photoluminescence spectroscopy and X-ray analysis. All iridium complexes were tested for their ability as photosensitisers to promote homogeneously catalysed hydrogen generation from water. In the presence of [HNEt(3)][HFe(3)(CO)(11)] as a water-reduction catalyst (WRC) and triethylamine as a sacrificial reductant (SR), seven of the new iridium complexes showed activity. [Ir(6-iPr-bpy)(ppy)(2)]PF(6) (bpy: 2,2'-bipyridine, ppy: 2-phenylpyridine) turned out to be the most efficient photosensitiser. This complex was also tested in combination with other WRCs based on rhodium, platinum, cobalt and manganese. In all cases, significant hydrogen evolution took place. Maximum turnover numbers of 4550 for this Ir-PS and 2770 for the Fe WRC generated in situ from [HNEt(3)][HFe(3)(CO)(11)] and tris[3,5-bis(trifluoromethyl)phenyl]phosphine was obtained. These are the highest overall efficiencies for any Ir/Fe water-reduction system reported to date. The incident photon to hydrogen yield reaches 16.4% with the best system.     

Controlling phosphorescence color and quantum yields in cationic iridium complexes: a combined experimental and theoretical study

We report a combined experimental and theoretical study on cationic Ir(III) complexes for OLED applications and describe a strategy to tune the phosphorescence wavelength and to enhance the emission quantum yields for this class of compounds. This is achieved by modulating the electronic structure and the excited states of the complexes by selective ligand functionalization. In particular, we report the synthesis, electrochemical characterization, and photophysical properties of a new cationic Ir(III) complex, [Ir(2,4-difluorophenylpyridine)2(4,4'-dimethylamino-2,2'-bipyridine)](PF(6)) (N969), and compare the results with those reported for the analogous [Ir(2-phenylpyridine)2(4,4'-dimethylamino-2,2'-bipyridine)](PF(6)) (N926) and for the prototype [Ir(2-phenylpyridine)2(4,4'-tert-butyl-2,2'-bipyridine)](PF(6)) complex, hereafter labeled N925. The three complexes allow us to explore the (C/\N) and (N/\N) ligand functionalization: considering N925 as a reference, we investigate in N926 the effect of electron-releasing substituents on the bipyridine ligand, while in N969, we investigate the combined effect of electron-releasing substituents on the bipyridine ligand and the effect of electron-withdrawing substituents on the phenylpyridine ligands. For N969 we obtain blue-green emission at 463 nm with unprecedented high quantum yield of 85% in acetonitrile solution at room temperature. To gain insight into the factors responsible for the emission color change and the different quantum yields, we perform DFT and TDDFT calculations on the ground and excited states of the three complexes, characterizing the excited-state geometries and including solvation effects on the calculation of the excited states. This computational procedure allows us to provide a detailed assignment of the excited states involved in the absorption and emission processes and to rationalize the factors determining the efficiency of radiative and nonradiative deactivation pathways in the investigated complexes. This work represents an example of electronic structure-driven tuning of the excited-state properties, thus opening the way to a combined theoretical and experimental strategy for the design of new iridium(III) phosphors with specific target characteristics.     

Synthesis and characterization of new iridium photosensitizers for catalytic hydrogen generation from water

Novel phenylazole ligands were applied successfully in the synthesis of cyclometalated iridium(III) complexes of the general formula [Ir(phenylazole)(2)(bpy)]PF(6) (bpy=2,2'-bipyridine). All complexes were fully characterized by NMR, IR, and MS spectroscopic studies as well as by cyclic voltammetry. Three crystal structures obtained by X-ray analysis complemented the spectroscopic investigations. The excited-state lifetimes of the iridium complexes were determined and showed to be in the range of several hundred ns to multiple μs. All obtained iridium complexes were active as photosensitizers in catalytic hydrogen evolution from water in the presence of triethylamine as a sacrificial reducing agent. Applying an in situ formed iron-based water reduction catalyst derived from [HNEt(3)](+) [HFe(3)(CO)(11)](-) and tris[3,5-tris-(trifluoromethyl)-phenyl]phosphine as the ligand, [Ir(2-phenylbenz-oxazole)(2)-(bpy)]PF(6) proved to be the most efficient complex giving a quantum yield of 16% at 440 nm light irradiation.     

Ruthenium(II) complexes containing bis(2-(diphenylphosphino)phenyl) ether and their catalytic activity in hydrogenation reactions

The half-sandwich complexes [(eta5-C5H5)RuCl(DPEphos)] (1) and [{(eta6-p-cymene)RuCl2}2(mu-DPEphos)] (2) were synthesized by the reaction of bis(2-(diphenylphosphino)phenyl) ether (DPEphos) with a mixture of ruthenium trichloride trihydrate and cyclopentadiene and with [(eta6-p-cymene)RuCl2]2, respectively. Treatment of DPEphos with cis-[RuCl2(dmso)4] afforded fac-[RuCl2(kappa3-P,O,P-DPEphos)(dmso)] (3). The dmso ligand in 3 can be substituted by pyridine, 2,2'-bipyridine, 4,4'-bipyridine, and PPh3 to yield trans,cis-[RuCl2(DPEphos)(C5H5N)2] (4), cis,cis-[RuCl2(DPEphos)(2,2'-bipyridine)] (5), trans,cis-[RuCl2(DPEphos)(mu-4,4'-bipyridine)]n (6), and mer,trans-[RuCl2(kappa3-P,P,O-DPEphos)(PPh3)] (7), respectively. Refluxing [(eta6-p-cymene)RuCl2]2 with DPEphos in moist acetonitrile leads to the elimination of the p-cymene group and the formation of the octahedral complex cis,cis-[RuCl2(DPEphos)(H2O)(CH3CN)] (8). The structures of the complexes 1-5, 7, and 8 are confirmed by X-ray crystallography. The catalytic activity of these complexes for the hydrogenation of styrene is studied.     

Efficient yellow electroluminescence from a single layer of a cyclometalated iridium complex

We report on the spectroscopic, electrochemical, and electroluminescent properties of [Ir(ppy)(2)(dtb-bpy)](+)(PF(6))(-) (ppy: 2-phenylpyridine, dtb-bpy: 4,4'-di-tert-butyl-2,2'-dipyridyl). Single-layer devices were fabricated and found to emit yellow light with a brightness that exceeds 300 cd/m(2) and a luminous power efficiency that exceeds 10 Lm/W at just 3 V. The PF(6)(-) space charge was found to dominate the device characteristics.     

Novel dinuclear luminescent compounds based on iridium(III) cyclometalated chromophores and containing bridging ligands with ester-linked chelating sites

The syntheses and study of the spectroscopic, redox, and photophysical properties of a new set of species based on Ir(III) cyclometalated building blocks are reported. This set includes three dinuclear complexes, that is, the symmetric (with respect to the bridging ligand) diiridium species [(ppy)(2)Ir(mu-L-OC(O)-C(O)O-L)Ir(ppy)(2)][PF(6)](2) (5; ppy = 2-phenylpyridine anion; L-OC(O)-C(O)O-L = bis[4-(6'-phenyl-2,2'-bipyridine-4'-yl)phenyl]-benzene-1,4-dicarboxylate), the asymmetric diiridium species [(ppy)(2)Ir(mu-L-OC(O)-L)Ir(ppy)(2)][PF(6)](2) (3; L-OC(O)-L = 4-([(6'-phenyl-2,2'-bipyridine-4'-yl)benzoyloxy]phenyl)-6'-phenyl-2,2'-bipyridine), and the mixed-metal Ir-Re species [(ppy)(2)Ir(mu-L-OC(O)-L)Re(CO)(3)Br][PF(6)] (4). Syntheses, characterization, and spectroscopic, photophysical, and redox properties of the model mononuclear compounds [Ir(ppy)(2)(L-OC(O)-L)][PF(6)] (2) and [Re(CO)(3)(L-COOH)Br] (6; L-COOH = 4'-(4-carboxyphenyl)-6'-phenyl-2,2'-bipyridine) are also reported, together with the syntheses of the new bridging ligands L-OC(O)-L and L-OC(O)-C(O)O-L. The absorption spectra of all the complexes are dominated by intense spin-allowed ligand-centered (LC) bands and by moderately intense spin-allowed metal-to-ligand charge-transfer (MLCT) bands. Spin-forbidden MLCT absorption bands are also visible as low-energy tails at around 470 nm for all the complexes. All the new species exhibit metal-based irreversible oxidation and bipyridine-based reversible reduction processes in the potential window investigated (between +1.80 and -1.70 V vs SCE). The redox behavior indicates that the metal-based orbitals are only weakly interacting in dinuclear systems, whereas the two chelating halves of the bridging ligands exhibit noticeable electronic interactions. All the complexes are luminescent both at 77 K and at room temperature, with emission originating from triplet MLCT states. The luminescence properties are temperature- and solvent-dependent, in accord with general theories: emission lifetimes and quantum yields increase on passing from acetonitrile to dichloromethane fluid solution and from room-temperature fluid solution to 77 K rigid matrix. In the dinuclear mixed-chromophore species 3 and 4, photoinduced energy transfer across the ester-linked bridging ligands seems to occur with low efficiency.     

Room temperature borylation of arenes and heteroarenes using stoichiometric amounts of pinacolborane catalyzed by iridium complexes in an inert solvent

Aromatic C-H borylation of arenes and heteroarenes using stoichiometric amounts of pinacolborane was catalyzed by an iridium complex generated from 1/2[Ir(OMe)(COD)]2 and 4,4'-di-tert-butyl-2,2'-bipyridine at room temperature in hexane and afforded the corresponding aryl- and heteroarylboronates in high yields with excellent regioselectivities.     

Phenomenally high molar extinction coefficient sensitizer with "donor-acceptor" ligands for dye-sensitized solar cell applications

A phenomenally high molar extinction coefficient heteroleptic ruthenium(II) complex [Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-(4-{4-methyl-2,5-bis[3-methylbutoxy]styryl}-2,5-bis[3-methylbutoxy]-2,2'-bipyridine)(NCS) 2] ( DCSC13) was synthesized by incorporating donor-acceptor ligands. The absorption spectrum of the DCSC13 sensitizer is dominated by metal-to-ligand charge-transfer transitions (MLCT) in the visible region, with absorption maxima appearing at 442 and 554 nm. The lowest MLCT absorption bands are red-shifted, and the molar extinction coefficients of these bands are significantly higher at 72,100 and 30,600 M(-1) cm(-1), respectively, when compared to those of the analogous [Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-dimethyl-2,2'-bipyridine)(NCS)2] (N820) sensitizer. The DCSC13 complex, when anchored on nanocrystalline TiO 2 films, exhibited increased short-circuit photocurrent and consequent power-conversion efficiency when compared with the N820 sensitizer.     

Dipyridylketone as a versatile ligand precursor for new cationic heteroleptic cyclometalated iridium complexes

Three new bis-cyclometalated iridium(III) complexes, of general formula [Ir(2-phenylpyridine)(2)(L)](+), are reported. The compounds contain a dipyridine-type ligand (L) derived from di-2-pyridylketone (dipyridin-2-ylmethanol, 2,2'-(hydrazonomethylene)dipyridine and 3-hydroxy-3,3-di(pyridine-2-yl)propanenitrile) and were synthesized through two different reaction pathways. The alternative synthetic pathway herein proposed, namely the direct reactions on the complex [Ir(2-phenylpyridine)(2)(2,2'-dipyridylketone)](+), overcame the inconveniences encountered with the standard reaction between the dimeric precursor [Ir(2-phenylpyridine)(2)(μ-Cl)](2) and the ancillary ligands (L). The photophysical characterization of the iridium complexes reveals that modifications on the ancillary ligand introduce large changes in the photophysical behaviour of the complexes. High emission quantum yield is associated with the presence of a saturated carbon between the two pyridyl moieties: [Ir(2-phenylpyridine)(2)(2,2'-dipyridylketone)](+) and [Ir(2-phenylpyridine)(2)(2,2'-(hydrazonomethylene)dipyridine)](+) are extremely low emissive, while [Ir(2-phenylpyridine)(2)(dipyridin-2-ylmethanol)](+) and [Ir(2-phenylpyridine)(2)(3-hydroxy-3,3-di(pyridine-2-yl)propanenitrile)](+) are good photoemitters. DFT and TD-DFT calculations confirmed the mixed LC/MLCT character of the excited states involved in the absorption and emission processes and highlighted the role of the π-conjugation between the two subunits of the ancillary ligand in determining the nature of the LUMO.     

Panchromatic sensitization of nanocrystalline TiO2 with cis-Bis(4-carboxy-2-[2'-(4'-carboxypyridyl)]quinoline)bis(thiocyanato-N)ruthenium(II)

We compared the spectral (IR and Raman), electrochemical, and photoelectrochemical properties of nanocrystalline TiO(2) sensitized with the newly synthesized complex [NBu(4)](2)[cis-Ru(Hdcpq)(2)(NCS)(2)] (1; [NBu(4)](+) = tetrabutylammonium cation; H(2)dcpq = 4-carboxy-2-[2'-(4'-carboxypyridyl)]quinoline) with those of TiO(2) sensitized with [NBu(4)](2)[cis-Ru(Hdcbpy)(2)(NCS)(2)] (2; H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) and [NBu(4)](2)[cis-Ru(Hdcbiq)(2)(NCS)(2)] (3; H(2)dcbiq = 4,4'-dicarboxy-2,2'-biquinoline). Complex 1 achieved efficient sensitization of nanocrystalline TiO(2) films over a wide visible and near-IR region, generating a large short-circuit photocurrent. The absorbed photon-to-current conversion efficiency decreased in the order 2 > 1 > 3 with the decrease in the free energy change (-Delta G(inj)) of the electron injection from the ruthenium complex to TiO(2). The open-circuit photovoltages (V(oc)'s) of dye-sensitized solar cells decreased in the order 2 > 1 > 3 with the increase in the dark current resulting from reverse electron transfer from TiO(2) to I(3)(-). The sensitizer-dependent V(oc) value can be interpreted as a result of reverse electron transfer through the sensitizing dye molecules.     

Synthesis, functionalization, characterization, and photophysical study of carbonyl-containing isocyano rhenium(I) diimine complexes

New classes of tunable rhenium(I) diimine luminophores with formula of [Re(CO)(CNR)(3)(N-N)]PF(6) and [Re(CO)(L(x))(CNC(6)H(4)Cl-4)(2)(1,10-phenanthroline)]PF(6), (R = C(6)H(5), 4-BrC(6)H(4), 4-ClC(6)H(4), 4-MeOC(6)H(4), 2,6-(i)Pr(2)C(6)H(3); N-N = 1,10-phenanthroline, 5,6-dibromo-1,10-phenanthroline, 4,4'-di-tert-butyl-2,2'-bipyridine; L(x) = MeCN, pyridine and PPh(3)) have been synthesized. Different synthetic routes including photo-ligand substitution and thermal carbonyl ligand substitution through the oxidative decarbonylation with trimethyl amine N-oxide, for the facial and meridional isomeric forms of [Re(CO)(CNR)(3)(N-N)]PF(6) were investigated. On the basis of these synthetic strategies, different ligand modification and functionalization of the rhenium(I) diimine luminophores with tailored excited state properties could be readily achieved. The structures of both facial and meridional conformations of [Re(CO)(CNR)(3)(N-N)]PF(6) and the complex precursors fac-[Re(CO)(3)(CNC(6)H(3)(i)Pr-2,6)(3)]OTf were determined by X-ray crystallography. These complexes display an orange to red (3)MLLCT [dπ(Re) → π*(N-N)] phosphorescence at room temperature. Detailed photophysical investigations revealed that the physical, photophysical, electrochemical, and excited state properties can be fine-tuned and tailored through the modifications of the substituents on isocyanide or diimine ligands.     

The intramolecular aryl embrace: from light emission to light absorption

6-(1-Methylpyrrol-2-yl)-2,2'-bipyridine, 3, and 6-(selenophene-2-yl)-2,2'-bipyridine, 4, have been prepared and characterized in solution and by structural determinations. Copper(I) complexes [CuL(2)][PF(6)] in which L is 2,2'-bipyridine substituted in the 6-position by furyl, thienyl, N-methylpyrrolyl, selenopheneyl, methyl or phenyl, (L = 1-6) have been synthesized. The complexes have been characterized by electrospray mass spectrometry, and solution NMR and UV-VIS spectroscopies. The single crystal structures of [Cu(1)(2)][PF(6)], [Cu(2)(2)][PF(6)], [Cu(3)(2)][PF(6)], [Cu(5)(2)][PF(6)] and [Cu(6)(2)][PF(6)] have been determined. In those compounds containing an aromatic substituent attached to the bpy unit, the substituent is twisted with respect to the latter. In [Cu(3)(2)][PF(6)] and [Cu(5)(2)][PF(6)], this results in intra-cation π-stacking between ligands which is very efficient in [Cu(3)(2)](+) despite the steric requirements of the N-methyl substituents. Face-to-face stacking between the ligands in the [Cu(2)(2)](+) ion is achieved by complementary substituent twisting and elongation of one Cu-N bond, but there is no analogous intra-cation π-stacking in [Cu(1)(2)](+). Ligand exchange reactions between [CuL(2)][PF(6)] (L = 1-6) and TiO(2)-anchored ligands 7-10 (L' = 2,2'-bipyridine-based ligands with CO(2)H or PO(OH)(2) anchoring groups) have been applied to produce 24 surface-anchored heteroleptic copper(i) complexes, the formation of which has been evidenced by using MALDI-TOF mass spectrometry and thin layer solid state diffuse reflectance electronic absorption spectroscopy. The efficiencies of the complexes as dyes in DSCs have been measured, and the best efficiencies are observed for [CuLL'] with L' = 10 which contains phosphonate anchoring groups.     

Synthesis of panchromatic Ru(II) thienyl-dipyrrin complexes and evaluation of their light-harvesting capacity

Ru(II) complexes with 5-(3-thienyl)-4,6-dipyrrin (3-TDP), containing 2,2'-bipyridine (bpy) or 4,4'-bis(methoxycarbonyl)-2,2'-bipyridine (dcmb) as coligands, have been prepared and extensively characterized. Crystal structure determination of [Ru(bpy)(2)(3-TDP)]PF(6) (1a) and [Ru(bpy)(3-TDP)(2)] (2) reveals that the 3-thienyl substituent is rotated with respect to the plane of the dipyrrinato moiety. These complexes, as well as [Ru(dcmb)(2)(3-TDP)]PF(6) (1b), act as panchromatic light absorbers in the visible range, with two strong absorption bands observable in each case. A comparison to known Ru(II) complexes and quantum-chemical calculations at the density functional theory (DFT) level indicate that the lower-energy band is due to metal-to-ligand charge transfer (MLCT) excitation, although the frontier occupied metal-based molecular orbitals (MOs) contain significant contributions from the 3-TDP moiety. The higher energy band is assigned to the π-π* transition of the 3-TDP ligand. Each complex exhibits an easily accessible one-electron oxidation. According to DFT calculations and spectroelectrochemical experiments, the first oxidation takes place at the Ru(II) center in 1a, but is shifted to the 3-TDP ligand in 1b. An analysis of MO energy diagrams suggests that complex 1b has potential to be used for light harvesting in the dye-sensitized (Gr?tzel) solar cell.     

New pyrazolino- and pyrrolidino[60]fullerenes with transition-metal chelating pyridine substitutents: synthesis and complexation to Ru(II)

Three pyridine-substituted fullerene adducts, bis(2,2'-bipyridine)(2'-phenyl-5'-(2-pyridinyl)-2'H-[5,6]fullereno(C(60)-I(h))[1,9]pyrazole)ruthenium-bis(hexafluorophosphate) (1), bis(2,2'-bipyridine)(2'-phenyl-5'-(4-(4'-methyl-2,2'-bipyridinyl))-2'H-[5,6]fullereno(C(60)-I(h))[1,9]pyrazole)ruthenium-bis(hexafluorophosphate) (2), and bis(2,2'-bipyridine)(1',5'-dihydro-3'-methyl-2'-(4-(4'-methyl-2,2'-bipyridinyl))-2'H-[5,6]fullereno(C(60)-I(h))[1,9]pyrrole)ruthenium-bis(hexafluorophosphate) (3), have been prepared. The common features for these complexes are the short bridges between the fullerene and the pyridine moieties. [structure: see text]