Thienyl-BOPHY dyes as promising templates for bulk heterojunction solar cells.

The synthesis and characterization of bis(difluoroboryl)-1,2-bis((1H-pyrrol-2-yl)methylene)hydrazone functionalized with two lateral vinyl-thienyl modules and exhibiting strong absorption in the 400-800 nm window in thin films are reported. Bulk heterojunction solar cells assembled with these dyes and a fullerene derivative (PC71BM), using very small quantities of the additive diiodooctane, give a power conversion efficiency as high as 4.3% with short-circuit current values of 10.9 mA cm(-2), an open-circuit voltage of 0.7 V and external quantum efficiencies higher than 70% over a broad range of wavelengths (580 to 720 nm).

New ligands bearing chiral bioactive fragments.

[see reaction]. Reliable and practical synthetic routes for the construction of hybrid molecules bearing both a chelating center and a useful biofunction are presented. They comprise the sequential cross-coupling reaction between ethynylated synthons with iodo-substituted L-tyrosine derivatives and provide access to various rationally designed chiral ligands.

Synthesis of quasi-linear and segmented bis- to penta-2, 2'-bipyridine polytopic ligands built via a convergent approach

Reliable and practical routes for the preparation of segmented oligomeric 2,2'-bipyridine-based ligands possessing rigid and conjugated spacers are presented. The first series of ligands bears a single alkyne function as a bridge and has been built by Pd(0)-catalyzed cross-coupling reactions between ethynylated and bromo-substituted derivatives of 2,2'-bipyridine (bipy). These new ligands provide access to numerous hexameric, octameric, and decameric pyridine-based materials. Optimum conditions were found with [Pd(PPh(3))(4)] (6 mol %) in benzene containing diisopropylamine at 80 degrees C. The second series of soluble ligands was synthesized around a 1,4-diethynyl-2, 5-didodecyloxybenzene bridging unit. The synthesis required a protection/deprotection methodology, as well as a chemioselective palladium-catalyzed Sonogashira-Hagihara cross-coupling protocol to obtain the target multitopic ligands. Within this strategy, the pivotal 15b, 17, and 19b intermediates bearing one or two bipy and phenyl units are required and such entities have been isolated in excellent yield. The products are highly soluble and photostable. In each case, the final step involves a double cross-coupling reaction between the appropriate constituents, with the best preparative conditions involving [Pd(PPh(3))(4)] (6 mol %) in n-propylamine at 70 degrees C. The main advantage of this methodology lies in its synthetic versatility and adaptability for creating multitopic metal-binding scaffolds with a potentially large variety of bridging units and phenyl substituents. Spectroscopic data for the new oligomers show a steady decrease in optical energy with an increasing degree of oligomerization. The different results obtained with these ligands highlight the importance of the rigid 1, 4-diethynylphenyl linker in directing the outcome of the nanosized molecules.

Synthesis of soluble bis-terpyridine ligands bearing ethynylene-phenylene spacers

Soluble and rigid terpyridine-based ditopic ligands bearing one to five phenylene/ethynylene modules have been synthesized by way of a stepwise procedure. Each module is attached to the terpyridine unit via an ethynylene fragment and functionalized at the 4-position with an additional ethynylene connector and in the 2,5-positions with two flexible dodecyloxy chains. The synthetic protocol is based on sequential Pd(0)-catalyzed cross-coupling reactions between a terpyridine subunit grafted with the necessary diethynyl/phenyl or ethynylphenyl/bromide appendage. For ditopic ligands displaying an even number of phenyl/ethynylene modules, the final step involves a single cross-coupling reaction between 4'-ethynylene-2,2':6',6' '-terpyridine and the appropriate bromo derivative. In the case of the ligands having an odd number of phenylene/ethynylene fragments, a double cross-coupling reaction between an extended dibromopolyphenylene intermediate and 4'-ethynylene-2,2':6',6' '-terpyridine or 1-(4'-ethynylene-2,2':6',2' '-terpyridine)-4-ethynylene-2,5-didodecyloxy-benzene is required. For ligands I-V, optimal preparative conditions were found with [Pd(0)(PPh(3))(4)] (6 mol %) in n-propylamine at 70 degrees C. Oxidative dimerization of the 1-(4'-ethynylene-2,2':6',2' '-terpyridine)-4-ethynylene-2,5-didodecyloxybenzene derivative in the presence of cupric salts and oxygen gives the corresponding homoditopic ligand II(2)() bearing a central diphenyldiacetylene spacer. Spectroscopic data for the new oligomers are discussed in terms of the extent of pi-electron conjugation. Upon increasing the number of phenylene/ethynylene modules, there is a progressive lowering in energy of absorption and fluorescence transitions.

Facile synthesis of polypyridine esters: A route to functionalized aldehydes

A wide range of ester-substituted oligopyridines, based on pyridine, 1,8-naphthyridine, 1,10-phenanthroline, 2,2'-bipyridine, and 2,2':6', 6' '-terpyridine units, has been synthesized and fully characterized. The principal reaction involves the palladium(0)-catalyzed carboalkoxylation of the bromo-, chloro- or triflate-substituted pyridine unit with carbon monoxide in the presence of a primary alcohol as nucleophile and a tertiary amine as base. Monofunctionalization of disubstituted compounds is realized by reaction in ethanol under mild conditions (70 degrees C, 1 atm CO). Stepwise reduction of selected esters with sodium borohydride, followed by Swern oxidation, affords the corresponding carbaldehydes in good yield. Several products are reported for the first time. The synthetic methods reported herein represent a valuable approach to the large-scale preparation of ester-functionalized oligopyridines that can be subsequently transformed to the corresponding alcohols or acids. These procedures also provide a practical methodology to the rational design of ligands bearing different kinds of functionalities.

Controlling Electronic Communication in Ethynylated-Polypyridine Metal Complexes.

By introduction of a naphthalene subunit in the middle of a butadiynylene spacer the triplet lifetime of the ruthenium chromophore in RR is prolongated to 475 ns. By increasing laser intensities the two Ru-terpy terminals are simultaneously promoted to the triplet state, and triplet - triplet annihilation occurs. In contrast, in the mixed Ru/Os complex (RO) the long inherent triplet lifetime of the Os-terpy fragment facilitates reverse triplet energy transfer. terpy=bis(2,2':6',2"-terpyridine).

Photochemical generation of carbon monoxide and hydrogen by reduction of carbon dioxide and water under visible light irradiation.

Visible light irradiation of solutions of Ru(2,2'-bipyridine)(3) (2+), cobalt(II) chloride, and carbon dioxide in acetonitrile/water/triethylamine generates simultaneously carbon monoxide and hydrogen. The reaction involves photoinduced reduction of CO(2) and H(2)O, triethylamine serving as electron donor in the Ru(2,2'-bipyridine)(3) (2+)/Co(2+) system. The amount of gas (CO + H(2)) produced and the selectivity ratio CO/H(2) depend markedly on the composition of the system. Addition of free bipyridine strongly decreases CO generation but increases H(2) production. With different tertiary amines, NR(3), both the quantity (CO + H(2)) and the ratio CO/H(2) increase markedly along the sequence R = methyl, ethyl, propyl. Higher selectivity for CO(2) reduction to CO in preference to water reduction occurs when triethanolamine is used instead of triethylamine. CoCl(2) is the most efficient mediator for both CO and H(2) generation and specifically promotes CO formation, whereas salts of other cations studied only yield H(2). The mechanism of the reaction may involve intermediate formation of Co(I) species. These processes represent an abiotic photosynthetic system allowing simultaneous generation of CO and H(2) and regulation of the CO/H(2) ratio. Mechanistic studies and explorations of other components that may increase efficiency and product selectivity should be carried out. The results obtained are also of significance for solar energy conversion with consumption of a pollutant, CO(2).

Magnetic and electronic properties in novel terpyridine-based nitroxide complexes: strong radical-metal interaction via a pyridyl ring.

Transition metal complexes of 2-[4'-(2,2':6',2' '-terpyridyl)]-(4,4,5,5-tetramethylimidazolinyl-3-oxide-1-oxyl) (terpy-NIT) and 2-[4'-(2,2':6',2' '-terpyridyl)]-(4,4,5,5-tetramethylimidazolinyl-1-oxyl) (terpy-IM) have been prepared. Whereas the pyridyl fragments of the free ligands are in an anti conformation, the complexes are obtained by coordination of two terpyridines in a syn conformation, forming a distorted octahedron around the metal center: [M(terpy-NIT)(2)](ClO(4))(2) (M = Ni(II) 1, Zn(II) 2, Cu(II) 3) and [M(terpy-IM)(2)](ClO(4))(2) (M = Ni(II) 4, Zn(II) 5). The ligands and their complexes have been characterized by FAB-MS, UV-vis, FT-IR spectroscopies, elemental analysis, and by EPR spectroscopy and susceptibility measurements. Single-crystal X-ray diffraction have been performed on the terpy-NIT ligand and on complexes 1, 4, and 5 giving following crystal data: terpy-NIT, monoclinic, P2(1)/c, Z = 4, a = 14.2186(5), b = 12.9129(6), c = 11.704(1) A, beta = 108.615(4) degrees; 1, orthorhombic, P(n a 2(1)), Z = 4, a = 23.6367(6), b = 8.7836(1), c = 24.2748(7) A; 4, monoclinic, P2(1), Z = 1, a = 8.738(1), b = 25.010(1), c = 11.704(1) A, beta = 102.849(3) degrees; 5, monoclinic, P2(1), Z = 1, a = 8.7463(2), b = 25.0833(5), c = 11.8168(3) A, beta = 102.757(3) degrees. For complexes 1 and 3, an antiferromagnetic behavior has been found and parametrized by considering a symmetric magnetic trimer, highlighting a strong intramolecular coupling between the metal and the radicals (average values 2J(M-NIT) = -19.6 K for M = Ni and -22.8 K for M = Cu). In the case of compound 4, an asymmetric magnetic trimer has been used to model the antiferromagnetic interactions (2J(Ni-IM1) = -13.0 K, 2J(Ni-IM2) = -5.6 K). The shape of the EPR spectra of complexes 2, 3, and 5 in solution indicates the intermediate exchange limit, of the order of a few mK, between the two nitroxide radicals through the pyridyl-metal-pyridyl fragment.

Mono- and dinuclear ruthenium(II) and osmium(II) polypyridine complexes built around spiro-bridged bis(phenanthroline) ligands: synthesis, electrochemistry, and photophysics.

Two new dyads have been synthesized in which terminal Ru(II) and Os(II) polypyridine complexes are separated by sterically constrained spiro bridges. The photophysical properties of the corresponding mononuclear complexes indicate the importance of the decay of the lowest-energy triplet states localized on the metallo fragments through the higher-energy metal-centered excited states. This effect is minimized at 77 K, where triplet lifetimes are relatively long, and for the Os(II)-based systems relative to their Ru(II)-based counterparts. Intramolecular triplet energy transfer takes place from the Ru(II)-based fragment to the appended Os(II)-based unit, the rate constant being dependent on the molecular structure and on temperature. In all cases, the experimental rate constant matches surprisingly well with the rate constant calculated for Förster-type dipole-dipole energy transfer. As such, the disparate rates shown by the two compounds can be attributed to stereochemical factors. It is further concluded that the spiro bridging unit does not favor through-bond electron exchange interactions, a situation confirmed by cyclic voltammetry.