Herein, a new aromatic carboxylate ligand, namely, 4-(dipyridin-2-yl)aminobenzoic acid (HL), has been designed and employed for the construction of a series of lanthanide complexes (Eu(3+) = 1, Tb(3+) = 2, and Gd(3+) = 3). Complexes of 1 and 2 were structurally authenticated by single-crystal X-ray diffraction and were found to exist as infinite 1D coordination polymers with the general formulas {[Eu(L)(3)(H(2)O)(2)]}(n) (1) and {[Tb(L)(3)(H(2)O)].(H(2)O)}(n) (2). Both compounds crystallize in monoclinic space group C2/c. The photophysical properties demonstrated that the developed 4-(dipyridin-2-yl)aminobenzoate ligand is well suited for the sensitization of Tb(3+) emission (Φ(overall) = 64%) thanks to the favorable position of the triplet state ((3)ππ*) of the ligand [the energy difference between the triplet state of the ligand and the excited state of Tb(3+) (ΔE) = (3)ππ* - (5)D(4) = 3197 cm(-1)], as investigated in the Gd(3+) complex. On the other hand, the corresponding Eu(3+) complex shows weak luminescence efficiency (Φ(overall) = 7%) due to poor matching of the triplet state of the ligand with that of the emissive excited states of the metal ion (ΔE = (3)ππ* - (5)D(0) = 6447 cm(-1)). Furthermore, in the present work, a mixed lanthanide system featuring Eu(3+) and Tb(3+) ions with the general formula {[Eu(0.5)Tb(0.5)(L)(3)(H(2)O)(2)]}(n) (4) was also synthesized, and the luminescent properties were evaluated and compared with those of the analogous single-lanthanide-ion systems (1 and 2). The lifetime measurements for 4 strongly support the premise that efficient energy transfer occurs between Tb(3+) and Eu(3+) in a mixed lanthanide system (η = 86%).

Three new binuclear lanthanide complexes of general formula [Ln 2 (L) 6 (H 2 O) 4 ] (Ln = Tb (1), Eu (2), and Gd (3)) supported by the novel aromatic carboxylate ligand 4-(dibenzylamino)benzoic acid (HL) have been synthesized. Complexes 1 and 2 were structurally characterized by single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic space group P 1 , and their molecular structures consist of homodinuclear species that are bridged by two oxygen atoms from two carboxylate ligands via different coordination modes. The discrete bridged dimer of 1 is centrosymmetric and features 8-coordinate terbium atoms, each of which adopts a distorted square-antiprismatic geometry. Both coordination spheres comprise two η 2 -chelating benzoates, two μ-η 1 :η 1 -carboxylate interactions from the bridging benzoates, and two water molecules. By contrast, in complex 2, the Eu 3þ ion coordination environment is best described as a distorted tricapped-trigonal prism, each europium ion being coordinated to three η 2 -chelating benzoate ligands and two water molecules. One of the η 2 -carboxylate ligands is involved in a further interaction with an adjacent metal, thus rendering the overall binding mode bridging tridentate, μ-η 2 :η 1 . Scrutiny of the packing diagrams for 1 and 2 revealed the existence of a one-dimensional molecular array that is held together by intermolecular hydrogen-bonding interactions. The Tb 3þ complex 1 exhibits high green luminescence efficiency in the solid state with a quantum yield of 82%. On the other hand, poor luminescence efficiency has been noted for the Eu 3þ -4-(dibenzylamino)benzoate complex.

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Herein, we have developed a series of isostructural mixed Ln(3+)-4-(dipyridin-2-yl)aminobenzoate coordination polymers [Ln(3+) = Eu(3+) (1), Tb(3+) (2), and Gd(3+) (3)], and characterized and investigated their photophysical properties. The results demonstrated that by gently tuning the excitation wavelength of these mixed lanthanide complexes, white light emission can be realized with the Commission Internationale de I'Eclairage coordinates (0.32, 0.34). Furthermore, by changing the concentration profiles of lanthanide ions stoichiometrically in mixed-lanthanide complexes and exciting at particular wavelengths, various emission colours can also be successfully obtained. The antenna ligand, 4-(dipyridin-2-yl)aminobenzoic acid, provides an efficient energy transfer for the sensitization of Eu(3+) and Tb(3+) complexes and exhibits red and green emissions, respectively. Most importantly, due to the high energy (32,150 cm(-1)) of the Gd(3+) ion lowest-lying emission level, the corresponding Gd(3+) complex displays ligand-centered visible emission in the blue light region, and hence it acts as a blue emitter. Therefore, Eu(3+) and Tb(3+) complexes in conjunction with a Gd(3+) complex is a suitable choice to obtain tunable white-light-emission from Ln(3+) coordination polymers. The morphological analyses of the mixed lanthanide coordination polymers by transmission electron microscopy (TEM) disclose that these compounds exist as unique crystalline nano-rods with an average diameter of 200 nm. The developed mixed lanthanide complexes also exhibit high thermal stability (~420 °C).

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Excited state energy and electron transfer processes in naphthalene and pyrene appended phosphorous(v) corroles.

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We report two corrole based donor–acceptor (D–A) dyads, Cbz-Cor and Ptz-Cor to understand the energy/electron transfer reactions. In these D–A systems, the donor, either carbazole (Cbz) or phenothiazine (Ptz), is covalently connected at the meso-phenyl position of 10-(phenyl)-5,15-bis-(pentafluorophenyl)corrole (Ph-Cor) by C–N linkage. Both the dyads were characterized by 1H NMR, MALDI-TOF MS, UV-vis, electrochemical, computational methods, study state fluorescence and TCSPC techniques. A comparison of absorption spectra with their reference monomeric compounds (Cbz-Ph, Ptz-Ph and Ph-Cor) revealed minimal ground-state interactions between chromophores in both dyads. Fluorescence studies suggested that singlet–singlet energy transfer from 1Cbz* to corrole is the major photochemical pathway in the Cbz-Cor dyad with a quenching efficiency of [Formula: see text]99%. Detailed analysis of the data suggests that Forster’s dipole–dipole mechanism does not adequately explain this energy transfer. However, at a 410 nm excitation, florescence quenching is detected in Ptz-Cor (49%) supporting a photo induced electron transfer (PET) process from the ground state of PTZ to the excited state of corrole macrocycle. The electron-transfer rates ([Formula: see text] of Ptz-Cor are found in the range [Formula: see text] to [Formula: see text] and are concluded to be solvent dependent.