Boyle Timothy J, Bunge Scott D, Clem Paul G, Richardson Jacob, Dawley Jeffrey T, Ottley Leigh Anna M, Rodriguez Mark A, Tuttle Bruce A, Avilucea Gabriel R, Tissot Ralph G
Sandia National Laboratories, Advanced Materials Laboratory, 1001 University Boulevard SE, Albuquerque, New Mexico 87105, USA.
Inorg Chem. 2005 Mar 7;44(5):1588-600. doi: 10.1021/ic048550b.
Using either an ammoniacal route, the reaction between DyCl3, Na0, and HOR in liquid ammonia, or preferentially reacting Dy(N(SiMe3)2)3 with HOR in a solvent, we isolated a family of dysprosium alkoxides as [Dy(mu-ONep)2(ONep)]4 (1), (ONep)2Dy[(mu3-ONep)(mu-ONep)Dy(ONep)(THF)]2(mu-ONep) (2), (ONep)2Dy[(mu3-ONep)(mu-ONep)Dy(ONep)(py)]2(mu-ONep) (3), [Dy3(mu3-OBut)2(mu-OBut3(OBut)4(HOBut)2] (4), [Dy3(mu3-OBut)2(mu-OBut)3(OBut)4(THF)2] (5), [Dy3(mu3-OBut)2(mu-OBut)3(OBut)4(py)2] (6), (DMP)Dy(mu-DMP)4[Dy(DMP)2(NH3)]2 (7), [Dy(eta6-DMP)(DMP)2]2 (8), Dy(DMP)3(THF)3 (9), Dy(DMP)3(py)3 (10), Dy(DIP)3(NH3)2 (11), [Dy(eta6-DIP)(DIP)2]2 (12), Dy(DIP)3(THF)2 (13), Dy(DIP)3(py)3 (14), Dy(DBP)3(NH3) (15), Dy(DBP)3 (16), Dy(DBP)3(THF) (17), Dy(DBP)3(py)2 (18), [Dy(mu-TPS)(TPS2]2 (19), Dy(TPS)3(THF)3 (20), and Dy(TPS)3(py)3 (21), where ONep = OCH2CMe3, OBut) = OCMe3, DMP = OC6H3(Me)(2)-2,6, DIP = OC6H3(CHMe2)(2)-2,6, DBP = OC6H3(CMe3)(2)-2,6, TPS = OSi(C6H5)3, tol = toluene, THF = tetrahydrofuran, and py = pyridine. We were not able to obtain X-ray quality crystals of compounds 2, 8, and 9. The structures observed and data collected for the Dy compounds are consistent with those reported for its other congeners. A number of these precursors were used as Dy dopants in Pb(Zr0.3Ti0.7)O3 (PZT 30/70) thin films, with compound 12 yielding the highest-quality films. The resulting Pb0.94Dy0.04(Zr0.3Ti0.7)O3 [PDyZT (4/30/70)] had similar properties to PZT (30/70), but showed substantial resistance to polarization reversal fatigue.
通过氨化途径，即DyCl₃、Na₀与HOR在液氨中的反应，或者更优选地使Dy(N(SiMe₃)₂)₃与HOR在溶剂中反应，我们分离出了一系列镝醇盐，如[Dy(μ-ONep)₂(ONep)]₄ (1)、(ONep)₂Dy[(μ₃-ONep)(μ-ONep)Dy(ONep)(THF)]₂(μ-ONep) (2)、(ONep)₂Dy[(μ₃-ONep)(μ-ONep)Dy(ONep)(py)]₂(μ-ONep) (3)、[Dy₃(μ₃-OBut)₂(μ-OBut)₃(OBut)₄(HOBut)₂] (4)、[Dy₃(μ₃-OBut)₂(μ-OBut)₃(OBut)₄(THF)₂] (5)、[Dy₃(μ₃-OBut)₂(μ-OBut)₃(OBut)₄(py)₂] (6)、(DMP)Dy(μ-DMP)₄[Dy(DMP)₂(NH₃)]₂ (7)、[Dy(η⁶-DMP)(DMP)₂]₂ (8)、Dy(DMP)₃(THF)₃ (9)、Dy(DMP)₃(py)₃ (10)、Dy(DIP)₃(NH₃)₂ (11)、[Dy(η⁶-DIP)(DIP)₂]₂ (12)、Dy(DIP)₃(THF)₂ (13)、Dy(DIP)₃(py)₃ (14)、Dy(DBP)₃(NH₃) (15)、Dy(DBP)₃ (16)、Dy(DBP)₃(THF) (17)、Dy(DBP)₃(py)₂ (18)、[Dy(μ-TPS)(TPS)₂]₂ (19)、Dy(TPS)₃(THF)₃ (20)和Dy(TPS)₃(py)₃ (21)，其中ONep = OCH₂CMe₃，OBut = OCMe₃，DMP = OC₆H₃(Me)₂-2,6，DIP = OC₆H₃(CHMe₂)₂-2,6，DBP = OC₆H₃(CMe₃)₂-2,6，TPS = OSi(C₆H₅)₃，tol = 甲苯，THF = 四氢呋喃，py = 吡啶。我们未能获得化合物2、8和9的X射线级质量的晶体。所观察到的镝化合物结构以及收集到的数据与报道的其他同系物的结构一致。这些前体中的一些被用作Pb(Zr₀.₃Ti₀.₇)O₃ (PZT 30/70)薄膜中的镝掺杂剂，化合物12产生了质量最高的薄膜。所得的Pb₀.₉₄Dy₀.₀₄(Zr₀.₃Ti₀.₇)O₃ [PDyZT (4/30/70)]具有与PZT (30/70)相似的性质，但对极化反转疲劳表现出显著的抗性。
