tris(acethylacetonato)terbium(III)

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tris(acethylacetonato)terbium(III)
• 英文别名: Tb(acac)₃；Tb(acetylacetonate)₃；Terbium-2,4-Pentanedionate；(Z)-4-oxopent-2-en-2-olate;terbium(3+)
• 化学式: C₁₅H₂₁O₆Tb
• 分子量: 456.254
• InChiKey: PJKGSRIANPFVEQ-LNTINUHCSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -0.48
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  120
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  selenium(IV) oxide 、 tris(acethylacetonato)terbium(III) 在 油胺 、 油酸 、 十八碳烯 、 三辛基膦 作用下， 反应 1.5h， 生成
  参考文献：
  名称：

  Liquid-Phase Syntheses and Material Properties of Two-Dimensional Nanocrystals of Rare Earth–Selenium Compound Containing Planar Se Layers: RESe₂ Nanosheets and RE₄O₄Se₃ Nanoplates

  摘要：

  Synthesis of diverse two-dimensional nanostructures with unique material properties is of current interest and multidisciplinary importance but remains a challenge for trivalent rare earth (RE)-selenium (Se) compounds because of the weak affinity between hard rare earth cations and soft selenium anions. In this article, for the first time, we report a mild solution approach toward a series of two-dimensional trivalent RE-selenium compounds nanocrystals, namely RESe2 nanosheets (RE = La to Nd, for EuSe2, nanobars were obtained) and RE4O4Se3 nanoplates (RE = Nd, Sm, Gd to Ho), under a high chemical potential of selenium obtained by activating SeO2 powder with oleylamine in high boiling point organic solvents. Both kinds of nanocrystals contain Se with -1 valence in planer Se layers, allowing for a great variability in their crystal structures. Satellite diffraction peaks were observed in the electron diffraction pattern of LaSe2 nanosheets, indicating the presence of Peierls distortion in the Se layers. In the RE4O4Se3 nanoplates, the interaction between Se2- ions and [Se-Se](2-) dumbbells in the Se layers increases when the radii of the RE3+ ions decrease along the lanthanide series, resulting in a narrower optical band gap (from 1.96 to 1.73 eV). The LaSe2 nanosheet films fabricated by drop-casting exhibited good electrical conductivity at room temperature (about 1 Omega.cm(-1)). Further, the RE4O4Se3 nanoplates showed very high light extinction capacity in the visible region (extinction coefficient mu(1); 4.4 x 10(5) cm(-1) for Nd4O4Se3, and 3.1 x 10(5) cm(-1) for Gd4O4Se3), comparable to that (5 x 10(5) cm(-1)) of CuInS2 commonly used in solar cells.

  DOI：

  10.1021/ja4028583
• 作为产物：
  描述：

  Tb(acac)3*H2O 生成 tris(acethylacetonato)terbium(III)
  参考文献：
  名称：

  乙酰丙酮稀土：新的制备方法和新的配合物

  摘要：

  已经开发出新的制备方法并将其用于制备几种新的稀土乙酰丙酮稀土络合物。据报道无水钕和三乙酰丙酮euro的晶体形式和无水镧，钕，sa 、,、,和三乙酰丙酮ter的无定形形式。还制备了钕和euro配合物的一元衍生物。描述了配合物的光谱，物理和化学性质。观察到结晶和无定形无水化合物的性质存在明显差异。

  DOI：

  10.1016/0022-1902(77)80059-6
• 作为试剂：
  描述：

  四丁基溴化铵 、 1,2-二氰基苯 在 tris(acethylacetonato)terbium(III) 、 苄基三乙基氯化铵 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 正己醇 、 甲醇 为溶剂， 反应 0.5h， 以664 mg的产率得到[N(C4H9)4][bis(phthalocyaninato)terbium(III)]
  参考文献：
  名称：

  Spin Dynamics in the Negatively Charged Terbium (III) Bis-phthalocyaninato Complex

  摘要：

  The experimental and theoretical study of the electron spin dynamics in the anionic form of a single-ion molecule magnet (SIMM), the bis-phthalocyaninato terbium (III) molecule [Pc2Tb](-)[TBA](+), has been addressed by means of solid state H-1 NMR spectroscopy. The magnetic properties of the caged Tb3+ metal center were investigated in a series of diamagnetically diluted preparations, where the excess of tetrabutylamonium bromide ([TBA]Br)(n) salt was used as diamagnetic matrix complement. We found that a high temperature activated spin dynamics characterizes the systems, which involved phonon-assisted transitions among the crystal field levels in qualitative agreements with literature results. However, the activation barriers in these processes range from 641 cm(-1) for the diamagnetically diluted samples to 584 cm-1 for those undiluted; thus, they exhibit barriers 2-3 times larger than witnessed in earlier (230 cm-1) reports (e.g., Ishikawa, N.; Sugita, M.; Ishikawa, T.; Koshihara, S.; Kaizu, Y. J. Am. Chem. Soc. 2003, 125, 8694-8695). At cryogenic temperatures, fluctuations are driven by tunneling processes between the m = +6 and -6 low-energy levels. We found that the barrier A and the tunneling rates change from sample to sample and especially the diamagnetically diluted [Pc2Tb](-) molecules appear affected by the sample's magneto/thermal history. These observations emphasize that matrix arrangements around [Pc2Tb](-) can appreciably alter the splitting of the crystal field levels, its symmetry, and hence, the spin dynamics. Therefore, understanding how small differences in molecular surroundings (as for instance occurring by depositing on surfaces) can trigger substantial modifications in the SIMM property is of utmost importance for the effective operation of such molecules for single-molecule data storage, for example.

  DOI：

  10.1021/ja808649g

文献信息

• Electrochemistry of lanthanoid(III) complexes in dimethyl sulfoxide in the presence of n-Bu4N(acac) and n-Bu4N(dibm)
  作者：Akio Iwase、Yoshinori Araki、Reiko Takahashi

  DOI：10.1016/0013-4686(90)87070-i

  日期：1990.11

  lanthanoid Ln(III) complexes was investigated in Me2SO including n-Bu4N(acac) and n-Bu4N(dibm) as ligands (where acac is the acetylacetonate anion and dibm is the diisobutrylmethanate anion). Reversible one electron reduction waves corresponding to Ln(III) complexes→Ln(II) complexes were observed in the concentration range of 5–20 mM of the ligands, including 1 mM lanthanoid perchlorates and 0.1 M TEAP

  镧系LN（III）络合物的电化学行为在我研究了2 SO包括Ñ -Bu 4 N（ACAC）和Ñ -Bu 4 N（dibm）作为配体（其中ACAC是乙酰丙酮化物阴离子和dibm是diisobutrylmethanate阴离子） 。在5–20 mM的配体浓度范围内观察到了对应于Ln（III）配合物→Ln（II）配合物的可逆的一个电子还原波，包括1 mM镧系高氯酸盐和0.1 M TEAP。在存在5 mM配体的情况下，在0.1 M TEAP中，镧系元素络合物的半波电势为sce -1.66至-2.61 V ，具体取决于镧系元素（III）离子。
• Efficient scrambling-free synthesis of heteroleptic terbium triple-decker (porphyrinato)(crown-phthalocyaninates)
  作者：Kirill P. Birin、Yulia G. Gorbunova、Aslan Yu. Tsivadze

  DOI：10.1039/c2dt30841j

  日期：——

  New heteroleptic triple-decker terbium complexes of general structure [Br4TPP]Tb[(15C5)4Pc]Tb[Br4TPP] (Tb-TD) and [Br4TPP]Tb[(15C5)4Pc]Tb[(15C5)4Pc] (Tb-TD*) (Br4TPP = tetrakis-meso-(4-bromophenyl)-porphyrin, (15C5)4Pc = tetra-(15-crown-5)-phthalocyanine) are synthesized with 48% and 57% yields, respectively. The triple-decker complexes were prepared by interaction of generated in situ terbium monoporphyrinate [Br4TPP]Tb(acac) and corresponding double-decker precursors. The heteroleptic double-decker precursor [Br4TPP]Tb[(15C5)4Pc] was prepared for the first time in a two step one-pot synthesis. No ligand scrambling was observed in the synthesis of Tb-TD, while 4% scrambling was determined in the case of Tb-TD*. High yields of target triple-decker complexes were achieved despite the presence of electron-donating crown-ether fragments with low thermal stability at the phthalocyanine deck. Analysis of lanthanide-induced paramagnetic shifts of protons of Tb-TD together with data of previously reported La, Pr, Nd and Eu analogues allowed precise separation of contributions of contact and dipolar lanthanide terms as well as verification of isostructurality of complexes within the series.

  新型异配位三层铽复合物，结构一般为 [Br4TPP]Tb[(15C5)4Pc]Tb[Br4TPP] (Tb-TD) 和 [Br4TPP]Tb[(15C5)4Pc]Tb[(15C5)4Pc] (Tb-TD*) （Br4TPP = 四取代-美索-(4-溴苯基)-卟啉，(15C5)4Pc = 四-(15-冠-5)-酞菁），合成的产率分别为48%和57%。这些三层复合物是通过原位生成的铽单卟啉盐 [Br4TPP]Tb(acac) 与相应的双层前驱体相互作用制备的。异配位双层前驱体 [Br4TPP]Tb[(15C5)4Pc] 是首次采用两步一锅法合成的。在Tb-TD的合成过程中未观察到配体重排，而在Tb-TD*的合成中观察到4%的重排。尽管在酞菁层中存在具有低热稳定性的电子给体冠醚片段，目标三层复合物的高产率仍得以实现。对Tb-TD质子在镧系元素引起的顺磁性位移的分析，以及已报告的La、Pr、Nd和Eu类似物的数据，使得精确分离接触和偶极镧系项的贡献成为可能，并验证了该系列复合物的同构性。
• Reactivity of the europium hexafluoroacetylacetonate (hfac) complex, Eu(hfac)3(diglyme), and related analogs with potassium: formation of the fluoride hfac “ate” complexes, [LnF(hfac)3K(diglyme)]2
  作者：William J. Evans、Dimitrios G. Giarikos、Matthew A. Johnston、Michael A. Greci、Joseph W. Ziller

  DOI：10.1039/b104095m

  日期：2002.2.5

  The europium hexafluoroacetylacetonate complex Eu(hfac)3(diglyme) was synthesized to examine its fluorescence and conversion to a Eu(II) analog. Reaction of Eu(hfac)3(diglyme) with potassium produced the unexpected trivalent product [EuF(hfac)3K(diglyme)]2. This reduction system was studied further by synthesizing other Ln(hfac)3(diglyme) analogs and examining their reactivity with potassium. The Nd, Sm, and Gd analogs of Ln(hfac)3(diglyme) also react with potassium to form [LnF(hfac)3K(diglyme)]2 as observed for europium. Reactions of the Eu(II) precursors, EuI2(thf)4 and [Zr2(OiPr)9]Eu(μ-I)}2 with K(hfac) also form trivalent products, namely Eu(hfac)3(diglyme) and [Zr2(OiPr)9]Eu(hfac)2.

  我们合成了六氟乙酰丙酮酸铕络合物 Eu(hfac)3(二甘醇)，以研究其荧光和向 Eu(II)类似物的转化。Eu(hfac)3(diglyme) 与钾反应产生了意想不到的三价产物 [EuF(hfac)3K(diglyme)]2。通过合成其他 Ln(hfac)3(二甘醇)类似物并检验它们与钾的反应性，进一步研究了这种还原体系。Ln(hfac)3(二甘醇)的 Nd、Sm 和 Gd 类似物也与钾反应生成[LnF(hfac)3K(二甘醇)]2，与铕的反应相同。Eu(II)前体 EuI2(thf)4 和 [Zr2(OiPr)9]Eu(δ-I)}2 与 K(hfac)的反应也会形成三价产物，即 Eu(hfac)3(diglyme) 和 [Zr2(OiPr)9]Eu(hfac)2。
• First X-ray crystal structure of a lanthanide(iii) monoporphyrinic complex using non-planar porphyrin rings
  作者：Georgios A. Spyroulias、Alexis Despotopoulos、Catherine P. Raptopoulou、Aris Terzis、Athanassios G. Coutsolelos

  DOI：10.1039/a608013h

  日期：——

  Twenty-three years after the first synthesis of lanthanide(III) porphyrins the X-ray crystal structure of [Tb III (β-Cl 8 tpp)(O 2 CMe)(Me 2 SO 2 ] is reported; the synthetic route to four halogenated porphyrins H 2 (β-X n tpp) (X = Cl or Br, n = 4 or 8) is described and compared with the corresponding [Tb III (β-X n tpp)(O 2 CMe)]; the highly distorted structure of the Tb III complex is compared with similar perhalogenated porphyrinic complexes; the X-ray structure of the brominated free base is also reported.

  在首次合成镧系(III)卟啉 23 年后，报告了[Tb III (β-Cl 8 tpp)(O 2 CMe)(Me 2 SO 2 ]的 X 射线晶体结构；描述了四种卤代卟啉 H 2 (β-X n tpp) (X = Cl 或 Br, n = 4 或 8) 的合成路线，并与相应的[Tb III (β-X n tpp)(O 2 CMe)] 进行了比较； 将 Tb III 复合物的高度畸变结构与类似的全卤化卟啉复合物进行了比较；还报告了溴化游离碱的 X 射线结构。
• The preparation and characterization of some anhydrous rare earth trisacetylacetonates
  作者：Janice K. Przystal、William G. Bos、Ivan B. Liss

  DOI：10.1016/0022-1902(71)80465-7

  日期：1971.3

  Anhydrous trisacetylacetonate complexes of yttrium, gadolinium, terbium, dysprosium, holmium and erbium have been prepared. Melting points, heats of fusion and i.r., visible and u.v. spectra are reported for these compounds and compared with the properties of the corresponding trihydrates. Additional properties reported are the PMR spectrum of the yttrium compound and the fluorescence spectrum of the

  制备了钇，ado，ter，、,和的无水三乙酰丙酮配合物。报告了这些化合物的熔点，熔融热以及红外光谱，可见光谱和紫外光谱，并将其与相应三水合物的性质进行了比较。报道的其他性质是钇化合物的PMR光谱和b化合物的荧光光谱。无水化合物在潮湿的空气中水解，得到碱性衍生物。对于无水化合物，提出了其中金属离子为8-配位的二聚结构。