Coordination of {Mo142} Ring to La3+ Provides Elliptical {Mo134La10} Ring with a Variety of Coordination Modes

Materials

Eri Ishikawa¹  Yutaka Yano¹ 

[1] Chemical Resources Laboratory, Tokyo Institute of Technology, R1-21, 4259 Nagatsuta, Midori-ku, Yokohama 226–850, Japan

关键词: {Mo₁₄₂}- ring;    elliptical {Mo₁₃₄La₁₀}-ring;    Mo-blues molecular design;    La³⁺-coordination geometry;    X-ray crystal structure;    isothermal titration calorimetry (ITC);    ¹³⁹La-NMR;   

DOI  :  10.3390/ma3010064

来源: mdpi

【 摘 要 】

A 28-electron reduced C_2h-Mo-blue 34Ǻ outer ring diameter circular ring, [Mo₁₄₂O₄₂₉H₁₀(H₂O)₄₉(CH₃CO₂)₅(C₂H₅CO₂)]^30- (≡{Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}) comprising eight carboxylate-coordinated (with disorder) {Mo₂} linkers and six defect pockets in two inner rings (four and three for each, respectively), reacts with La³⁺ in aqueous solutions at pH 3.5 to yield a 28-electron reduced elliptical C_i-Mo-blue ring of formula [Mo₁₃₄O₄₁₆H₂₀(H₂O)₄₆{La(H₂O)₅}₄{La(H₂O)₇}₄{LaCl₂(H₂O)₅}₂]^10- (≡{Mo₁₃₄La₁₀}), isolated as the Na₁₀[Mo₁₃₄O₄₁₆H₂₀(H₂O)₄₆{La(H₂O)₅}₄{La(H₂O)₇}₄{LaCl₂(H₂O)₅}₂]·144 H₂O Na⁺ salt. The elliptical structure of {Mo₁₃₄La₁₀} showing 36 and 31 Å long and short axes for the outer ring diameters is attributed to four (A-D) modes of LaO₉/LaO₇Cl₂ tricapped-trigonal-prismatic coordination (TTP) geometries. Two different LaO₂(H₂O)₇ and one LaO₂(H₂O)₂Cl₂ TTP geometries (as A-C modes) for each of two inner rings result from the coordination of all three defect pockets of the inner ring for {Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}, and two LaO₄(H₂O)₅ TTP geometries (as D mode) result from the displacement of two (acetate/propionate-coordinated) binuclear {Mo₂} linkers with La³⁺ in each inner ring. The isothermal titration calorimetry (ITC) of the ring modification from circle to ellipsoid, showing the endothermic reaction of [La³⁺]/[{Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}] = 6/1 with ΔH = 22 kJ⋅mol^-1, ΔS = 172 J⋅K^-1⋅mol^-1, ΔG = −28 kJ⋅mol^-1, and K = 9.9 × 10⁴ M^-1 at 293 K, leads to the conclusion that the coordination of the defect pockets to La³⁺ precedes the replacement of the {Mo₂} linkers with La³⁺. ¹³⁹La- NMR spectrometry of the coordination of {Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)} ring to La³⁺ is also discussed.

【 授权许可】

CC BY   
© 2010 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland.