A Panchromatic Cyclometalated Iridium Dye Based on 2-Thienyl-Perimidine.

Though 2-arylperimidines have never been used in iridium(III) chemistry, the present study on structural, electronic and optical properties of N-unsubstituted and N-methylated 2-(2-thienyl)perimidines, supported by DFT/TDDFT calculations, has shown that these ligands are promising candidates for construction of light-harvesting iridium(III) complexes. In contrast to N-H perimidine, the N-methylated ligand gave the expected cyclometalated µ-chloro-bridged iridium(III) dimer which was readily converted to a cationic heteroleptic complex with 4,4'-dicarboxy-2,2'-bipyridine. The resulting iridium(III) dye exhibited panchromatic absorption up to 1000 nm and was tested in a dye-sensitized solar cell.

Overcoming the Inertness of Iridium(III) in a Facile Single-Crystal to Single-Crystal Reaction of Iodine Vapor with a Cyclometalated Chloride Monomer.

Iridium(III) is often considered to be one of the most inert octahedral metal ions. Herein we present a phenanthroimidazole-based bis-cyclometalated iridium(III) chloride undergoing a facile chloro ligand exchange with iodine, in a gas-solid reaction under ambient conditions. Monitoring the progress of the reaction by X-ray diffraction analysis reveals the crystal-packing-induced exceptional stereoselectivity of this topochemical transformation. The results provide excellent opportunities to modulate the geometry and kinetic properties of cyclometalated iridium(III) complexes that may be very promising in catalysis and design of anticancer agents.

Rational design of efficient photosensitizers based on cyclometalated iridium(III) complexes with 2-arylbenzimidazole and aromatic 1,3-diketone ligands.

A judicious selection of substituents in cyclometalating 2-arylbenzimidazoles and an ancillary aromatic 1,3-diketone enabled the creation of heteroleptic iridium(III) complexes demonstrating strong light absorption up to 500 nm (ε ≈ 10 000-12 000 M-1 cm-1). The complexes, which were studied by various spectroscopic techniques, single-crystal X-ray diffraction and cyclic voltammetry, displayed tunable absorption maxima depending on the nature of substituents and their positions. The experimental study was corroborated by quantum chemical calculations, which showed an increased contribution of intraligand charge transfer transitions to the visible light absorption in the case of complexes containing electron-withdrawing substituents in the ligands. Despite being of high intensity, some of these transitions are responsible for the formation of the excited states located at large distances from the 'anchoring' fragment incorporated in the ancillary ligand. In turn, incorporation of electron-donating substituents at the para-position to the Ir-C bonds increases the number of excited states located on the ancillary ligand. The destabilization of the HOMO, which is caused by the increase in the electron-donating ability of the substituents in the metalated rings, translated into negative shifts of the Ir4+/Ir3+ redox potential, affecting, in some cases, the degree of electrochemical reversibility of the complexes. Several complexes having strong light-harvesting characteristics and undergoing reversible oxidation in the appropriate potential range were used for coating the TiO2 photoanodes, which reached an efficiency of 2.15% upon irradiation with the standard AM 1.5 spectrum.

Tailoring the π-system of benzimidazole ligands towards stable light-harvesting cyclometalated iridium(III) complexes.

The synthesis, structure, optical and redox properties as well as photovoltaic studies of iridium(III) complexes with cyclometalated 2-arylbenzimidazoles decorated with various polyaromatic fragments and an ancillary aromatic ß-diketone are reported. Despite the strong preference of the iridium(III) ion to form bis- or tris-cyclometalated complexes in which the metal participates in five-membered metallacycles, the cyclometalation of the benzimidazole ligands containing rigid π-extended systems yields dimeric complexes containing strained five- or six-membered metallacycles and allows for generating an extremely rare monocyclometalated complex. X-ray crystallography shows that the steric strain observed in the dimers is retained in heteroleptic diketonate complexes which is also corroborated by gas-phase DFT calculations. While emission maxima and redox potentials of the heteroleptic complexes exhibit just a moderate variation upon the change of the cyclometalated ligands, the extension of the π-system of the benzimidazole ligands give the complexes remarkable light absorption in the visible spectral range, which meets the requirements for application in dye-sensitized solar cells. At the titania photoanodes, these iridium dyes retain their optical properties and exhibit power conversion efficiencies under standard AM 1.5 G conditions comparable to those of other iridium-based sensitizers. These results demonstrate that the size and position of the π-extended fragment in cyclometalated ligands can modulate not only the electronic structure of the corresponding iridium(III) complexes, but also affect their composition, structure and reactivity that may find implications in future design of emerging iridium dyes, emitters and catalysts.

Syntheses and crystal structures of 2-(p-tol-yl)-1H-perimidine hemihydrate and 1-methyl-2-(p-tol-yl)-1H-perimidine.

The title compounds, 2-(4-methylphenyl)-1H-perimidine hemihydrate (1, C18H14N2·0.5H2O) and 1-methyl-2-(4-methylphenyl)-1H-perimidine (2, C19H16N2), were prepared and characterized by 1H NMR and single-crystal X-ray diffraction. The organic mol-ecule of the hemihydrate lies on a twofold rotation axis while the water mol-ecule lies on the inter-section of three twofold rotation axes (point group symmetry 222). As a consequence, the hydrogen atoms that are part of the N-H group and the water mol-ecule as well as the CH3 group of the p-tolyl ring are disordered over two positions. In compound 1, the perimidine and the 2-aryl rings are slightly twisted while its N-methyl-ated derivative 2 has a more distorted conformation because of the steric repulsion between the N-methyl group and the 2-aryl ring. In the crystal structures, mol-ecules of perimidine 2 are held together only by C-H⋯π contacts while the parent perimidine 1 does not exhibit this type of inter-action. Its crystal packing is established by inter-molecular N-H⋯O hydrogen bonds with the solvent water mol-ecules and additionally stabilized by π-π stacking.

Synthesis and crystal structures of N-H, N-phenyl and N-benzyl-2-(4-hexyl-oxyphen-yl)benzimidazoles.

The title compounds, 2-(4-hexyl-oxyphen-yl)-1H-benzimidazole (C19H22N2O; 1), 2-(4-hexyl-oxyphen-yl)-1-phenyl-1H-benzimidazole (C25H26N2O; 2) and 1-benzyl-2-(4-hexyl-oxyphen-yl)-1H-benzimidazole (C26H28N2O; 3) were synthesized and their structures were determined by single-crystal X-ray analysis. The N-substituent at the imidazole moiety slightly affects the inter-planar angle between the 4-hexyl-oxyphenyl ring and the benzimidazole system. The unsubstituted benzimidazole (1) forms inter-molecular N-H⋯N bonds while in the crystal structures of 2 and 3, the mol-ecules are assembled only through π-π and C-H⋯π inter-actions.

Synthesis and comparative structural study of 2-(pyridin-2-yl)-1H-perimidine and its mono- and di-N-methyl-ated analogues.

The title compounds, 2-(pyridin-2-yl)-1H-perimidine (C16H11N3; 1), 1-methyl-2-(pyridin-2-yl)-1H-perimidine (C17H13N3; 2), and 1,3-dimethyl-2-(pyridin-2-yl)-1H-perimidinium iodide (C18H16N3 +·I-; 3) were synthesized under mild conditions and their structures were determined by 1H NMR spectroscopy and single-crystal X-ray analysis. The N-methyl-ation of the nitro-gen atom(s) at the perimidine moiety results in a significant increase of the inter-plane angle between the pyridin-2-yl ring and the perimidine system. The unsubstituted perimidine (1) forms a weak intra-molecular N-H⋯N bond that consolidates the mol-ecular conformation. In the crystal structures of 1-3, the mol-ecular entities all are assembled through π-π and C-H⋯π inter-actions.

Sterically hindered phenanthroimidazole ligands drive the structural flexibility and facile ligand exchange in cyclometalated iridium(III) complexes.

A series of bis-cyclometalated iridium(iii) complexes with 2-arylphenanthroimidazole "antenna" ligands containing electron-donor or withdrawing substituents and a more flexible ancillary aromatic ß-diketone bearing the "anchoring" carboxymethyl function has been prepared. Thorough X-ray study of the complexes revealed significant structural strains caused by bulky cyclometalated 2-arylphenanthroimidazoles resulting in dramatic distortions of the iridium octahedron and even in twist of the phenanthrene fragment. The crystal data were corroborated by gas-phase DFT calculations whereby the geometry of the complexes was distorted in the same way. While redox potentials, absorption and emission maxima of the complexes displayed expected change upon the variation of the electron-donating ability of the cyclometalated ligands, the complexes readily exchanged the bidentate ancillary ligand in the presence of a negligible amount of protons that was inspected in solution by UV-Vis spectroscopy. Moreover, after hydrolysis of the carboxymethyl group the resulting complexes readily react with the surface of titanium dioxide giving unique binuclear structures in which the deprotonated carboxy group of the coordinated ß-diketonate binds the second bis-cyclometalated unit by forming a four-membered metallacycle. Though the enhanced reactivity of the complexes is contrary to the common idea of the high inertness of iridium(iii) compounds it can be seen as a consequence of the interplay between the steric hindrance induced by the ligands and the strong preference of the iridium(iii) ion for octahedral geometry. This study demonstrates that the use of bulky ligands provides access to light-harvesting iridium(iii) complexes with required extent of lability which may be promising as photocatalysts and biologically active molecules.