Synthesis and characterization of a family of structurally characterized dysprosium alkoxides for improved fatigue-resistance characteristics of PDyZT thin films

Using either an ammoniacal route, the reaction between DyCl3, Na-0, 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)(2)Dy[(mu(3)-ONep)(mu-ONep)Dy(ONep)(THF)](2)(U-ONep) (2), (ONeP)(2)Dy[(mu(3)-ONep)(mu-ONep)Dy(ONep)(py)](2)(mu-ONep) (3), (Dy-3(mu(3)-OBut)(2)(mu-OBut)(3)(OBut)(4)(HOBut)(2)] (4), [Dy-3(mu(3)-OBut)(2)(mu-OBut)(3)(OBut)(4)(THF)(2)] (5), [Dy-3(mu(3)OBu)(2)(mu-OBut)(3)(OBut)(4) (py)(2)](6), (DMP)Dy(mu-DMP)(4)[Dy(DMP)(2)(NH3)](2) (7), [Dy(eta(6)-DMP)(DMP)(2)](2) (8), Dy(DMP)(3)(THF)(3) (9), Dy(DMP)(3)(py)(3) (10), Dy(DIP)(3)(NH3)(2) (11), [Dy(eta(6)-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(U-TPS)(TPS)(2)](2) (19), Dy(TPS)(3)(THF)(3) (20), and Dy(TPS)(3)(PY)(3) (21), where ONep = OCH2CMe3, OBut = OCMe3, DIVP OC6H3(Me)(2)-2,6, DIP = OC6H3(CHMe2)(2)-2,6, DBP = OC6H3(CM3)(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)O-3 (PZT 30/70) thin films, with compound 12 yielding the highest-quality films. The resulting Pb0.94Dy0.04(Zr0.3Ti0.7)O-3 [PDyZT (4/30/70)] had similar properties to PZT (30/70), but showed substantial resistance to polarization reversal fatigue.