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Volumn 46, Issue 16, 2007, Pages 6242-6244

Toward the rational design of lanthanide coordination polymers: A new topological approach

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EID: 34548033266     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic7009918     Document Type: Article
Times cited : (57)

References (25)
  • 1
    • 34548011387 scopus 로고    scopus 로고
    • Comprehensive Coordination Chemistry II; Elsevier Ltd.: Oxford, U.K., 2004; Vol. 3. Janiak, C
    • Kitagawa, S.; Noro, S. Comprehensive Coordination Chemistry II; Elsevier Ltd.: Oxford, U.K., 2004; Vol. 3. Janiak, C. Dalton Trans. 2003, 2781.
    • (2003) Dalton Trans , pp. 2781
    • Kitagawa, S.1    Noro, S.2
  • 21
    • 34548034371 scopus 로고    scopus 로고
    • To a solution of 6-(chloromethyl)pyridine-2-carboxyl ethyl ester (2.95 g, 14.8 mmol) in anhydrous acetonitrile (50 mL) were successfully added 1,4-diaminobutane dihydrochloride (0.582 g, 3.6 mmol) and K2CO 3 (3.45 g, 25 mmol, After refluxing for 20 h, the mixture was filtered. The solvent was evaporated to yield a yellow oil, which was dissolved in dichloromethane. The resulting solution was washed with water (2 x 100 mL) and then dried over anhydrous Na2SO4. After evaporation of the solvent, the resulting yellow oil (2.86 g) was refluxed overnight in a 6 M HCl solution (50 mL, After evaporation of the solvent to ∼5 mL, the solution was stored at 5°C overnight. A white solid was formed that was filtered, washed with 6 M HCl, and dried under vacuum to yield H 4tpabn·2HCl·6H2O (1.13 g, global yield 27, Elem anal. Calcd for H4tpabn·2HCl·6H2O C32H
    • 2py), 7.27 (4H, m, 4CH), 7.65 (m, 8H, 8CH).
  • 22
    • 34548039175 scopus 로고    scopus 로고
    • Synthesis of complex 1: A solution of TbCl3· 6H2O (18.58 mg, 0.050 mmol) in 4:1 EtOH/water (5 mL) was allowed to slowly diffuse into a 2:1 solution of TbCl3·6H2O (18.58 mg, 0.050 mmol) and H4tpabn (80.56 mg, 0.10 mmol) in water (9.0 mL) adjusted at pH, 6.5 (by the addition of Et3N, Three days later crystals suitable for X-ray diffraction formed. The crystals were filtered, washed with water, and dried under vacuum to yield [Tb(Htpabn)]·6H2O as a white crystalline powder (51.7 mg, 58, Elem anal. Calcd for [Tb(Htpabn)]·6H2O (C 32H41N6O14Tb, C, 43.06; H, 4.63; N, 9.41. Found: C, 43.1; H, 4.52; N, 9.49. A fraction of the solid was dried under vacuum at 130°C for 6 days to remove all of the water molecules. Calcd for [TbHtpabn, C32H29N6O8Tb, C, 48.99; H, 3.73; N, 10.71
    • 8Tb): C, 48.99; H, 3.73; N, 10.71. Found: C, 48.90; H, 3.81; N, 10.73.
  • 23
    • 34548036416 scopus 로고    scopus 로고
    • Crystal data for 1: [Tb(HTpabn)]·14H2O; C 32H57N6O22Tb, M, 1036.76 g/mol, monoclinic, space group P21/n, a, 16.0957(2) Å, b, 14.2869(1) Å, c, 18.4787(2) Å, β, 94.515(1)°, V, 4236.13(7) Å3, Z, 4, ρc, 1.626 g/cm3, μ, 1.76 mm-1, T, 100 K, Rint, 0.0384. Synchrotron radiation with λ, 0.710 76 Å and an MAR345 detector were used for data collection (SNBL at the ESRF, The structure was solved by direct methods and refined by a full-matrix least-squares technique on F2 using the SHELXL97 program: 597 refined parameters, R1, 0.0382 and wR2, 0.0902 for 8800 independent reflections with I > 2σ(I, R1, 0.0454 and wR2, 0.0951 for all 40 951 reflections, GOF, 1.017. H(C) atoms were modeled
    • 2 using the SHELXL97 program: 597 refined parameters, R1 = 0.0382 and wR2 = 0.0902 for 8800 independent reflections with I > 2σ(I); R1 = 0.0454 and wR2 = 0.0951 for all 40 951 reflections, GOF = 1.017. H(C) atoms were modeled in the riding model, while the H(N) atom was located from a difference Fourier map and refined independently. A total of 10 out of 28 H(O) atoms of water molecules were also located.
  • 25
    • 34548009022 scopus 로고    scopus 로고
    • Luminescence measurements were made on a Fluorolog FL 3-22 spectrometer from Spex-Jobin Yvon-Horiba, and quantum yields were determined by an absolute method using a home-built integration sphere.
    • Luminescence measurements were made on a Fluorolog FL 3-22 spectrometer from Spex-Jobin Yvon-Horiba, and quantum yields were determined by an absolute method using a home-built integration sphere.


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