A novel efficient antenna complex of Eu3+ [Eu(CPFHP)3(DDXPO)] supported by a highly fluorinated carbazole-substituted β-diketonate ligand, namely, 1-(9H-carbazol-2-yl)-4,4,5,5,5-pentafluoro-3-hydroxypent-2-en-1-one (CPFHP) and the 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide (DDXPO) ancillary ligand, has been synthesized, structurally characterized, and its photoluminescent behavior examined. The single-crystal X-ray diffraction analysis of Eu(CPFHP)3(DDXPO) revealed that this complex is mononuclear, and that the central Eu3+ ion is surrounded by eight oxygen atoms, six of which are provided by the three bidentate β-diketonate ligands. The remaining two oxygen atoms are furnished by the chelating phosphine oxide ligand. The coordination polyhedron is best described as that of a distorted square antiprism. The photophysical properties of Eu(CPFHP)3(DDXPO) benefit from adequate protection of the metal by the ligands with respect to non-radiative deactivation as well as an efficient ligand-to-metal ...

Highly luminescent poly(methyl methacrylate)-incorporated europium complex supported by a carbazole-based fluorinated β-diketonate ligand and a 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide co-ligand.

Luminescent lanthanide coordination polymers composed of lanthanide ions and organic joint ligands exhibit characteristic photophysical and thermostable properties that are different from typical organic dyes, luminescent metal complexes, and semiconductor nanoparticles. Various types of luminescent Eu(III) and Tb(III) coordination polymers have been reported to date. One-, two-, and three-dimensional alternating sequences of lanthanide ions and organic ligands exhibit remarkable characteristics as novel organic materials with various structures, and unique physical properties. In this review, the characteristic structures, photophysical properties, and photonic applications for organic display devices, triboluminescent materials, thermosensors, color and brightness tuning, new type organogels, future magneto-optical materials, luminescent organo-nanoparticles, and energy transfer process of lanthanide coordination polymers are introduced.

Luminescent lanthanide coordination polymers for photonic applications

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 (Eu3+ = 1, Tb3+ = 2, and Gd3+ = 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(H2O)2]}n (1) and {[Tb(L)3(H2O)].(H2O)}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 Tb3+ emission (Φoverall = 64%) thanks to the favorable position of the triplet state (3ππ*) of the ligand [the energy difference between the triplet state of the ligand and the excited state of Tb3+ (ΔE) = 3ππ* – 5D4 = 3197 cm–1], as investigated in the Gd3+ complex. On the other hand, the corresponding Eu3+ complex shows weak luminescence efficiency (Φoverall = 7%) due t...

Highly luminescent and thermally stable lanthanide coordination polymers designed from 4-(dipyridin-2-yl)aminobenzoate: efficient energy transfer from Tb3+ to Eu3+ in a mixed lanthanide coordination compound.

The 4f–4f emission of Tb(III), Eu(III), and Sm(III) complexes plays an important role in the design of monochromatic green, red, and deep-red luminescent materials for displays, lighting, and sensing devices. The 4f–4f emission of Yb(III), Nd(III), and Er(III) complexes is observed in the near-infrared (IR) region for bioimaging and security applications. However, their absorption coefficients are extremely small (e   10,000 L mol−1 cm−1) are introduced. Organic molecular design elements, including (1) the control of the excited triplet (T1) state, (2) the effects on the charge-transfer (CT) band, and (3) the energy transfer from metal ions for effective photosensitized luminescence, are explained. The characteristic electrosensitized luminescence (electroluminescence) and mechanoluminescence (triboluminescence) of lanthanide(III) complexes are also explained. Lanthanide(III) complexes with well-designed organic molecules are expected to open avenues of research among the fields of chemistry, physics, electronics, and material science. Lanthanide complexes can be made strongly luminescent by designing their ligands so that they act as antenna, find researchers in Japan. With their long luminescence lifetimes and narrow emission bands, lanthanide ions are attractive components for monochromatic luminescent materials. But their low light absorption hinders their widespread use. Yasuchika Hasegawa and co-workers from Hokkaido University, review how this problem can be overcome through using coordinating ligands as antennas. Such ligands absorb incident light and transfer its energy to the lanthanide ion. The researchers emphasize the importance of organic ligands’ excited triplet states and charge-transfer processes. They also discuss cases where luminescence is induced electrically or mechanically (for example, by grinding). The improved luminescence efficiency of such coordination complexes show promise for applications such as displays, solar cells and biomedical sensors. In this paper, the design strategy of trivalent lanthanide (Ln(III)) complexes for effective photo-, electric-, and tribo-sensitized luminescence are reviewed. Ln(III) complexes with well-designed organic molecules are expected to open up a frontier field of chemistry, physics, electronics and material science.

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Effective photosensitized, electrosensitized, and mechanosensitized luminescence of lanthanide complexes

Three new lanthanide heterocyclic β-diketonate complexes (Dy(PPI)3(EtOH)2 )( 1), (Dy(PPI)3(DPEPO)) (2), and (Tb(PPI)3(DPEPO)) (3 )( where HPPI =3 -phenyl-4- propanoyl-5-isoxazolone and DPEPO = b is(2- (diphenylphosphino)phenyl)ether oxide) have been synthesized and fully characterized. Single-crystal X-ray diffraction analyses reveal that these complexes are mononuclear and that the central Ln III ion is coordinated to eight oxygen atoms that are provided by three bidentate β-diketonate ligands and ethanol or bidentate DPEPO in a distorted square antiprismatic geometry. These complexes have high molar absorption coefficients (up to 3 × 10 4 M −1 cm −1 at 285 nm) and display strong visible and, for Dy III , NIR luminescence upon irradiation at the ligand-centered band in the range 250−350 nm. The emission quantum yields and the luminescence lifetimes at room temperature are 3 ± 0.5% and 15 ± 1 μs for 1 ,1 2± 2% and 33 ± 1 μs for 2, and 42 ± 6% and 795 ± 1 μs for 3. Moreover, the crystals of 2 and 3 exhibit brilliant triboluminescence, visible in daylight.

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Brilliant photoluminescence and triboluminescence from ternary complexes of Dy(III) and Tb(III) with 3-phenyl-4-propanoyl-5-isoxazolonate and a bidentate phosphine oxide coligand.

Two types of dimeric complexes [Ln2(hfa)6(i2-O(CH2)2NHMe2)2] and [Ln(thd)2(i2,e2-O(CH2)2NMe2)]2 (Ln ) YIII, EuIII, GdIII, TbIII, TmIII, LuIII; hfa- ) hexafluoroacetylacetonato, thd- ) dipivaloylmethanato) are obtained by reacting [Ln(hfa)3(H2O)2] and [Ln(thd)3], respectively, with N,N-dimethylaminoethanol in toluene and are fully characterized. X-ray single crystal analysis performed for the TbIII compounds confirms their dimeric structure. The coordination mode of N,N-dimethylaminoethanol depends on the nature of the â-diketonate. In [Tb2(hfa)6(i2-O(CH2)2NHMe2)2], eight-coordinate TbIII ions adopt distorted square antiprismatic coordination environments and are O-bridged by two zwitterionic N,N-dimethylaminoethanol ligands with a Tb1âââTb2 separation of 3.684(1) A. In [Tb(thd)2(i2,e2-O(CH2)2NMe2)]2, the N,N-dimethylaminoethanol acts as chelating-bridging O,N-donor anion and the TbIII ions are seven-coordinate; the Tb1âââTb1A separation amounts to 3.735(2) A within centrosymmetric dimers. The dimeric complexes are thermally stable up to 180 °C, as shown by thermogravimetric analysis, and their volatility is sufficient for quantitative sublimation under reduced pressure. The EuIII and TbIII dimers display metal-centered luminescence, particularly [Eu2(hfa)6(O(CH2)2NHMe2)2] (quantum yield QLn L ) 58%) and [Tb(thd)2(O(CH2)2NMe2)]2 (32%). Consideration of energy migration paths within the dimers, based on the study of both pure and EuIII- or TbIII-doped (0.01-0.1 mol %) LuIII analogues, leads to the conclusion that both the â-diketone and N,N-dimethylaminoethanol ligands contribute significantly to the sensitization process of the EuIII luminescence. The ancillary ligand increases considerably the luminescence of [Eu2(hfa)6(O(CH2)2NHMe2)2], compared to [Ln(hfa)3(H2O)2], through the formation of intra-ligand states while it is detrimental to TbIII luminescence in both â-diketonates. Thin films of the most luminescent compound [Eu2(hfa)6(O(CH2)2NHMe2)2] obtained by vacuum sublimation display photophysical properties analogous to those of the solid-state sample, thus opening perspectives for applications in electroluminescent devices.

Leonid S. Lepnev

Papers

Role of the Ancillary Ligand N,N-Dimethylaminoethanol in the Sensitization of EuIII and TbIII Luminescence in Dimeric β-Diketonates