RESUMO
A joint structural and spectroscopic study of simple bis-cyclometataled rhodium(III) and iridium(III) complexes with 2-phenylpyridine and aromatic ß-diketones (dibenzoylmethane, benzoylacetone, benzoyltrifluoroacetone, and 2-thenoyltrifluoroacetone) reveals an interplay between the solid-state emission efficiency and crystal packing peculiarities of the complexes. Although the prepared rhodium(III) cyclometalates are isostructural with iridium(III) analogues, different types of π-π interactions are responsible for the aggregation-induced emission (AIE) of the complexes depending on the metal ion. For iridium(III) complexes, pyridyl-pyridyl contacts are essential for AIE because they lower the energy of the emissive metal-to-ligand charge transfer state below that of the non-emissive state located at the ancillary ligand. Enabled by phenyl-pyridyl interactions partially blocking the population of non-emissive d-d states, solid-state phosphorescence enhancement is successfully achieved in a rhodium(III) complex with ancillary benzoyltrifluoroacetone, which is the first example of a rhodium complex exhibiting AIE.
RESUMO
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.
RESUMO
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-Hâ¯π contacts while the parent perimidine 1 does not exhibit this type of inter-action. Its crystal packing is established by inter-molecular N-Hâ¯O hydrogen bonds with the solvent water mol-ecules and additionally stabilized by π-π stacking.
RESUMO
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-Hâ¯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-Hâ¯π inter-actions.