Crystal Structure and Luminescence of Lanthanide Monodentate Complexes [Ln(C4N4H6O)2(H2O)6]Cl3 and [Ln(C4N4H6O)2(H2O)3(NO3)3] (Ln = Tb or Eu)

Author:

Law Ga-Lai1,Wong Ka-Leung1,Zhou Xianju1,Wong Wing-Tak1,Tanner Peter A.1

Affiliation:

1. Department of Chemistry, The University of Hong Kong, Hong Kong S.A.R., P. R. China, and Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong S.A.R., P.R. China

Publisher

American Chemical Society (ACS)

Subject

Inorganic Chemistry,Physical and Theoretical Chemistry

Reference10 articles.

1. Organo Lanthanide Metal Complexes for Electroluminescent Materials

2. Lanthanide-Containing Molecular and Supramolecular Polymetallic Functional Assemblies

3. 1 and 2.2,4-Diamino-6-hydroxy pyrimidine (L) (0.5 g, 3.96 mmol) was added to MeOH (25 mL) to give a cream solution. Upon addition of hydrated terbium chloride (1, 0.74 g, 1.98 mmol) or hydrated europium chloride (2, 0.74 g, 1.98 mmol), the solution changed to a clear yellow solution that was stirred for 24 h. The reaction in a 2:1 ratio afforded complexes1and2in high yields (1, 1.12 g, 90.4%;2, 1.03 g, 81.6%). Single, medium yellow crystals of the terbium complex suitable for X-ray study and microanalysis were obtained by slow evaporation from methanol.1:  Anal. Found:  C, 15.38; H, 3.85; N, 17.89. Calcd for [Tb(C4N4H6O)2(H2O)6]Cl3:  C, 15.35; H, 3.84; N, 17.91. IR (KBr, cm-1):  3446, 3331, 1642, 1485, 1465, 1351, 1309, 1257, 994, 800, 755, 688. ESI-MSm/z:  625.5 [M], 519 [M − 3Cl], 411 [M − 3Cl − 6H2O].2:  Anal. Found:  C, 15.57; H, 3.88; N, 18.12. Calcd for [Eu(C4N4H6O)2(H2O)6]Cl3:  C, 15.53; H, 3.91; N, 18.11; IR (KBr, cm-1):  3447, 3330, 1640, 1484, 1464, 1350, 1309, 1256, 994, 801, 687. ESI-MSm/z:  618.5 [M], 512 [M − 3Cl], 404 [M − 3Cl − 6H2O).3 and 4.L(0.5 g, 3.96 mmol) was added to MeOH (25 mL) to give a cream solution. Upon addition of the hydrated terbium nitrate (3, 0.90 g, 1.98 mmol) or hydrated europium nitrate (4, 0.88 g, 1.98 mmol), the solution changed to a clear solution. The resulting solution was stirred for 24 h. The reaction in a 2:1 ratio afforded complexes3and4in high yields (3, 0.98 g, 76.0%;4, 1.16 g, 91.0%). Single, medium yellow crystals of the europium complex suitable for X-ray study and microanalysis were obtained by slow evaporation from methanol.3:  Anal. Found:  C, 14.76; H, 2.75; N, 23.65. Calcd for [Tb(C4N4H6O)2(H2O)3(NO3)3]:  C, 14.75; H, 2.79; N, 23.66. IR (KBr, cm-1):  3442, 3353, 1642, 1384. ESI-MSm/z:  651 [M], 597 [M − 3H2O], 535 [M − 3H2O − NO3], 473 [M − 3H2O − 2NO3], 411 [M − 3H2O − 3NO3].4:  Anal. Found:  C, 14.91; H, 2.83; N, 23.92. Calcd for [Eu(C4N4H6O)2(H2O)3(NO3)3]:  C, 14.91; H, 2.82; N, 23.91. IR (KBr, cm-1):  3442, 3353, 1642, 1479, 1465, 1384, 1256. ESI-MSm/z:  644 [M], 590 [M − 3H2O], 528 [M − 3H2O − NO3], 467 [M − 3H2O − 2NO3], 404 [M − 3H2O − 3NO3].L:  IR (KBr, cm-1):  3431, 3353, 3240, 3168, 1653, 1497, 1467, 1376, 1303, 1249, 983, 783.

4. Crystal data for1:  [Tb(C4N4H6O)2(H2O)6]Cl3,M= 625.61, triclinic,P1̄ (No. 2),a= 9.084(5) Å,b= 10.772(8) Å,c= 12.959 (8) Å,V= 3775(1) Å3,T= 298 K,Z= 2, μ(Mo Kα) = 55.224 cm-1, 26 158 reflections measured, 5130 unique (Rint= 0.048), 4829 observed reflections [I> 2σ(I)] were used in all calculations.FtoR= 0.032,Rw= 0.038. CCDC 242 135. Crystal data for4:  [Eu(C4N4H6O)2(H2O)3(NO3)3],M= 644.26, triclinic,P1̄ (No. 2),a= 6.814(2) Å,b= 10.659(3) Å,c= 16.074 (5) Å,V= 1105.6 Å3,T= 298 K,Z= 2, μ(Mo Kα) = 55.224 cm-1, 26 158 reflections measured, 5130 unique (Rint= 0.048), 4829 observed reflections [I> 2σ(I)] were used in all calculations.FtoR= 0.019,Rw= 0.024. CCDC 251900.

5. Thiouracil Antithyroid Drugs as a New Class of Neuronal Nitric Oxide Synthase Inhibitors

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