238 resultados para LANTHANIDE


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We report an alternative medium of transparent upconverting colloid containing lanthanide ion doped NaYF4 nanocrystals for three-dimensional (3D) volumetric display. The colloids exhibit tunable upconversion luminescence with a wide spectrum of colors by adjusting the doping concentrations of the nanocrystals and the compositions of the colloids. Our preliminary experimental result indicates that an upconverting colloid-based 3D volumetric display using a convergent, near infrared laser beam to induce a localized luminescent spot near the focus is technically feasible. Therefore arbitrary 3D objects can be created inside the upconverting colloid by use of computer controlled 3D scanning systems. (C) 2008 Optical Society of America

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The structure and magnetic properties of the RCo5Ga7 (R = Y, Tb, Dy, Ho and Er) compounds with the ScFe6Ga6-type structure have been studied. The stability of RCo5Ga7 is closely related with the ratio of the metal radii R-RE/R-(Co,R-Ga). With R-RE/R-(Co,R-Ga) less than or equal to 1.36, the compounds can be stabilized in the ScFe6Ga6-type structure. The lattice of RCo5Ga7 shrinks as the atomic order of R increases, and it is consistent with the lanthanide contraction. The structure analysis based on X-ray diffraction patterns reveals that in the orthorhombic RCo5Ga7 (Immm), R occupies the 2a site, and Co enters into the 8k and the 4h sites, and Ga is at the 4e, 4f, 4g, 4h and 8k sites. The interatomic distances and the coordination numbers of RCo5Ga7 are provided from the refinement results. The short interatomic distance (less than 2.480 Angstrom) between the Co ions results in the negative magnetic interaction, which does not favor ferromagnetic ordering. The magnetic moment of YCo5Ga7 is absent, and RCo5Ga7 (R = Tb, Dy, Ho and Er) may have long-range magnetic ordering with the paramagnetic Curie temperature lower than 5 K. (C) 2004 Elsevier Inc. All rights reserved.

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The crystallographic and intrinsic magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) have been investigated. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions, mainly along the a- and b-axis rather than along the c-axis, are observed for all the compounds upon hydrogenation. Hydrogenation leads to an increase in Curie temperature. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and Tb(3)Fc(27.0)Cr(2.0)H(2.8), and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2 Abnormal crystallographic and magnetic properties of Ce3Fe29-xTxHy suggest that the Ce ion is non-triply ionized.

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A systematic study of the phase formation, structure and magnetic properties of the R3Fe29-xTx compounds (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) has been performed upon hydrogenation. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions mainly along the a- and b-axis rather than along the c-axis are observed for all of the compounds upon hydrogenation. Hydrogenation leads to an increase in the Curie temperature and a corresponding increase in the saturation magnetization at room temperature for each compound. First order magnetization processes (FOMP) occur in the external magnetic fields for Nd3Fe24.5Cr4.5H5.0, Tb3Fe27.0Cr2.0H2.8, and Gd3Fe28.0Cr1.0H4.2 compounds.

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A systematic investigation of crystallographic and intrinsic magnetic properties of the hydrides R3Fe29 - xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed in this work. The lattice constants a, b, and c and the unit cell volume of R3Fe29 - xVxHy decrease with increasing rare-earth atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in regular anisotropic expansions along the a-, b-, and c-axes in this series of hydrides. Abnormal crystallographic and magnetic properties of Ce3Fe27.5V1.5H6.5, like Ce3Fe27.5V1.5, suggest that the Ce ion is non-triply ionized. Hydrogenation leads to the increase in both Curie temperature for all the compounds and in the saturation magnetization at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Sm, Gd, and Dy, except for Tb. Hydrogenation also leads to a decrease in the anisotropy field at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Gd, Tb, and Dy, except for Sm. The Ce3Fe27.5V1.5 and Gd3Fe28.4V0.6 show the larger storage of hydrogen with y = 6.5 and 6.9 in these hydrides. (C) 1998 Elsevier Science B.V. All rights reserved.

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A systematic study of the structural and intrinsic magnetic properties of the hydrides R3Fe29-xCrxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. Hydrogenation lends to a relative volume expansion of the unit cell and a decrease in x-ray density for each compound. Anisotropic expansions mainly along the n- and b-axes rather than along the c-axis for all of the compounds upon hydrogenation are observed. The lattice constants and the unit-cell volume of R3Fe29-xCrx and R3Fe29-xCrxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in an increase in the Curie temperature and a corresponding increase in the saturation magnetization at room temperature for each compound. After hydrogenation a decrease of 0.34 mu(B)/Fe in the average Fe atomic magnetic moment and a slight increase in the anisotropy field for Y3Fe27.2Cr1.8 are achieved at 4.2 K. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and TD3Fe27.0Cr2.0H2.8, and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2. The abnormal crystallographic and magnetic properties of Ce3Fe25.0Cr4.0 and Ce3Fe25.0Cr4.0H5.4 suggest that the Ce ion non-triply ionized.

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A systematic investigation of crystallographic and magnetic properties of nitride R3Fe29-xCrxN4 (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. The lattice constants and unit cell volume decrease with increasing rare earth atomic number from Nd to Dy, reflecting the lanthanide contraction. After nitrogenation the relative volume expansion of each nitride is around between 5% and 7%. The nitrogenation results in a good improvement in the Curie temperature, the saturation magnetization and anisotropy fields at 4.2 K, and room temperature for R3Fe29-xCrxN4. Magnetohistory effects of R3Fe29-xCrxN4 and R3Fe29-xCrx (R=Nd and Sm) are observed in a low field of 0.04 T. First order magnetization process occurs in Sm3Fe24.0Cr5.0N4 in magnetic fields of 2.8 T at 4.2 K. After nitrogenation, the easy magnetization direction of Sm3Fe24.0Cr5.0 is changed from the easy-cone structure to the uniaxial. The good intrinsic magnetic properties of Sm3Fe24.0Cr5.0N4 make this compound a hopeful candidate for new high-performance hard magnets. (C) 1998 American Institute of Physics.

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A systematic investigation of crystallographic and magnetic properties of nitride R3Fe29-xVxN4 (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. Nitrogenation leads to a relative volume expansion of about 6%. The lattice constants and unit cell volume decrease with increasing rare-earth atomic number from Nd to Dy, reflecting the lanthanide contraction. On average, the Curie temperature increases due to the nitrogenation to about 200 K compared with its parent compound. Generally speaking, nitrogenation also results in a remarkable improvement of the saturation magnetization and anisotropy fields at 4.2 K and room temperature for R3Fe29-xVxN4 compared with their parent compounds. The transition temperature indicates the spin reorientations of R3Fe29-xVxN4 for R = Nd and Sm are at around 375 and 370 K which are higher than that of R3Fe29-xVx, for R = Nd and Sm 145 and 140 K, respectively. The magnetohistory effects of R3Fe29-xVxN4 (R = Ce, Nd, and Sm) are observed in low fields of 0.04 T. After nitrogenation the easy magnetization direction of Sm3Fe26.7V2.3 is changed from an easy-cone structure to the b-axis. As a preliminary result, a maximum remanence B-r of 0.94 T, an intrinsic coercivity mu(0)H(C) of 0.75 T, and a maximum energy product (B H)(max) of 108.5 kJ m(-3) for the nitride magnet Sm3Fe26.7V2.3N4 are achieved by ball-milling at 293 K.

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A systematic investigation of nitrides R3F29-xCrxN4 (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. The nitrogen concentration in the nitride R3Fe29-xCrxNy was determined to be y = 4. Nitrogenation leads to a relative volume expansion of about 5.3%. The lattice constants and unit cell volume decrease with increasing rare earth atomic number from Nd to Dy, reflecting the lanthanide contraction. In average, the increase of Curie temperature upon nitrogenation is about 200 K, compared with its parent compound. The nitrogenation also results in a remarkable improvement in the saturation magnetization and anisotropy fields for R3Fe29-x CrxN4 at 4.2 K and room temperature, compared with their parent compounds. A spin reorientation of Nd3Fe24.5Cr4.5N4 occurs at around 368 K, which is 138 K higher than that of Nd3F24.5Cr4.5. Magnetohistory effects of R3Fe29-xCrxN4 (R = Nd and Sm) are observed in a low field of 0.04 T. First-order magnetization process occurs in Sm3Fe24.0Cr5.0N4 in magnetic fields of around 3.0 T at 4.2 K. After nitrogenation the easy magnetization direction of Sm3Fe24.0C5.0 is changed from the easy-cone structure to the uniaxial. The excellent intrinsic magnetic properties of Sm3Fe24.0Cr5.0N4 make this compound a hopeful candidate for new high-performance permanent magnets.

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目前,国内外对于铕和铽等稀土配合物的可见区发光和应用都有大量研究,但对具有近红外发光(800-1700 nm)性能的稀土配合物的研究还处于起步阶段。由于稀土的近红外发光在光纤通讯、激光系统及诊断学等方面应用具有特殊的优点,越来越引起人们的兴趣和重视。 稀土近红外发光配合物的致命弱点是其光、热和化学稳定性较差,从而限制了其在很多领域的实际应用。而溶胶-凝胶材料和介孔材料具有良好的光、热和化学稳定性,能改善客体分子的结构环境和化学微环境,从而能有效提高客体分子的发光性能。因此,本论文将具有优良近红外发光性能的稀土配合物分别与上述两种基质复合,从实验和理论研究稀土近红外发光杂化材料的性能和应用价值,制备出具有良好稳定性的高效稀土近红外发光杂化材料,以期为光纤通讯、激光等领域提供潜在的候选材料。围绕这一宗旨,开展了如下工作: 通过原位技术分别得到了掺杂和嫁接[Ln(dbm)3phen]化合物(Ln = Er, Nd, Yb)的杂化凝胶材料,Ln-D-P gel和Xerogel-Ln。通过对其近红外发光性能的研究,表明材料中配体能很好的保护稀土离子,并将能量有效的传递给稀土离子。采用Judd-Ofelt理论对所得部分材料进行了光谱分析,基于实验数据和理论分析表明其具有潜在的光放大和激光应用价值。 选择了两种含全氟化烷基链的β-二酮配体Hhfth和Htfnb,通过功能化的phen-Si配体,将三元配合物[Ln(hfth)3phen] (Ln = Er, Nd, Yb, Sm)和[Pr(tfnb)3phen]成功共价嫁接到介孔MCM-41和SBA-15杂化材料中,得到的衍生材料Ln(hfth)3phen–MCM-41、Pr(tfnb)3phen–MCM-41和Ln(hfth)3phen–SBA-15、Pr(tfnb)3phen–SBA-15都保持了高度有序的介孔p6mm结构,并展现出稀土离子特征的近红外发射。所得稀土配合物功能化的材料的发射光谱能完全覆盖对光通讯极具应用价值的1300-1600nm区域。 通过对Er(dbm)3phen–M41(X, Y) (X = 1~14, Y = 3, 6, 12, 18, 24 h)材料系统的比较研究,选择了X = 12, Y = 6作为合成目标材料的优化参数,通过功能化的phen-Si配体将[Ln(dbm)3phen]配合物共价嫁接于有序介孔MCM-41和SBA-15中(Ln = Er, Nd, Yb),所得两类材料Ln(dbm)3phenM41和Ln(dbm)3phenS15都保持了很好的介孔有序性,并具有良好的近红外发光性能。通过对Ln(dbm)3phenM41和Ln(dbm)3phenS15两类材料发光行为的比较,以及两类材料中稀土离子的含量及孔结构的分析,推出以SBA-15为载体得到的材料在相对发光强度和荧光寿命上,均比以MCM-41为载体的材料有所提高。 通过对8-羟基喹啉配体进行改性,合成了具有双功能的配体Q-Si,继而合成了共价嫁接8-羟基喹啉衍生物的介孔杂化材料Q–SBA-15,其形貌均一,并具有高度有序的介孔p6mm结构。通过配体交换反应,得到了嫁接稀土喹啉配合物的具有近红外发光性能的介孔杂化材料LnQ3–SBA-15 (Ln = Er, Nd, Yb),其仍然保持高度有序的介孔结构,且外形呈现与母体材料Q–SBA-15相似的弯曲圆柱状。激发配体的吸收,LnQ3–SBA-15材料都分别展现出相应稀土离子特征的近红外发射,并详细分析和讨论了所得介孔杂化材料的近红外发光性能。

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稀土配合物的发光具有发射带窄、色纯度高、峰发光位置不受配体环境变化的影响、发光不受温度影响等特点,而且发射峰覆盖400-1800纳米的可见区和近红外区,因此可以作为有机电致发光器件的发光层材料。现在的研究大多集中于铕、铽配合物的电致发光器件研究,对于近红外稀土配合物的电致发光以及发白光的镝配合物研究相对较少,但是近红外发光的稀土铒、钕、镱在光通讯、激光技术、生物医学、荧光探针等方面具有特殊的应用前景。在本论文中主要阐述了新型稀土配合物的设计与合成、在器件方面的应用以及器件结构机理的研究。 在本论文中,我们主要研究吡唑酮的衍生物配体对于稀土离子的敏化激发作用。通过配体基团的改性,得到发光更有效的新型稀土配合物。首先,合成了配体PM,并选择TP、Phen、Bipy、Bath做第二配体制备镝、铒、钕、镱、钐等的配合物。解析了配合物的晶体结构,测试得到了各种配合物的光致发光性能,系统分析了几种配合物中配体到中心稀土离子的能量传递过程,研究了配体对稀土的敏化机制。其中镝配合物显示近白光的发射,色坐标为x=0.35,y=0.40,以此配合物为发光层的器件显示明亮的白光,最大发光亮度为527cd/m2,是目前已经报道的镝配合物器件中,性能最突出的一个。 设计合成了配体PT、PC、PF,利用TP和Bath做中性配体与镱离子形成配合物YbPT3Bath、YbPT3TP、YbPC3Bath,它们都显示977纳米的近红外发射。经过分析发现,配体对镱离子的敏化过程是通过电子转移的机制来完成的。通过几种镱配合物发光强度对比发现YbPT3Bath、YbPC3Bath的发射最强。首先将YbPT3Bath用于电致发光器件中,发现其具有较好的电子传输特性,而且YbPM3TP2具有较好的空穴传输特性。因此,我们将这两种配合物结合制备了双发光层电致发光器件,得到的器件比单发光层器件的性能提升了若干倍。我们认为,双发光层器件结构改善了载流子的传输和最终的复合,使得激子在发光层内形成,提高激子激发发光层材料的效率。最后,利用这种双发光层器件结构得到了辐照度比较理想的镱配合物近红外器件。 对ErPM3TP2、NdPM3TP2配合物的发光性能做了系统研究。首先,分析了它们的晶体结构,得到了具体的晶体参数和结构组成。二者在紫外区的吸收光谱都显示为配体的吸收,在紫外区之后出现了稀土离子的特征吸收峰,由此我们利用Judd-Ofelt理论分析计算了Er3+、Nd3+离子在这个配位环境中的振子强度参数,最后得到Er3+、Nd3+离子从激发态能级到下能级的电偶极跃迁辐射几率以及相应的自然寿命值。利用这两种配合物做为发光层材料制备了系列近红外电致发光器件,得到理想的辐照度强度,证明它们在制备近红外器件方面具有潜在应用价值。

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DNA是重要的生物大分子,也是主要的抗癌药物靶分子。小分子与DNA之间的相互作用是以DNA为靶分子的各种物质生物效应的基础,它们之间的特异性结合导致了癌变、突变及细胞的死亡。能够与DNA特异性结合的小分子很多都是临床上广泛应用的抗癌药物。因此,小分子与DNA之间的相互作用不论是对阐述抗癌、抗病毒药物的作用,还是对致癌机理的研究,尤其对抗癌药物的体内筛选都有重要意义。近十年来,开发新型的抗癌药物小分子,使它们具有对DNA序列特异性的识别能力己成为国内外研究的热点。斓系配合物由于具有广泛的光学、磁学和电学等特性使得有可能成为新的DNA特异性识别分子。然而,斓系离子在中性条件下极其容易水解的特性又极大的阻碍了斓系配合物对于DNA的识别性研究。本文在中性条件下合成了铜系氨基酸配合物,并成功的获得了这些配合物的晶体结构,利用这些有确定结构的I系氨基酸配合物与特定的DNA序列相作用,通过多种生物物理方法研究了它们对DNA序列特异性识别。主要的结果如下:1.在近中性条件下,合成了Eu-Val([Eus_8(L-HVal)_(16)(H_2O)_(32)]Cl_(24)·12.5H_2O),Eu-Asp([Eu_4(μ3-OH)_4(L-Asp)_2(L-HAsp)_3(H_2O)_7]Cl·11.5H_2O)和Tb-Cys(「Th_2(DL-Cys)_4(H_2O)_8]Cl_2)三种铜系氨基酸配合物,这些配合物的结构由于合成条件(温度,反离子及合成比例)上的差异与已报到的类似配合物的结构具有明显的不同。三种配合物的结构各具特色,从而在与DNA作用时将表现出各自特有的识别性能。2.Eu-Val配合物在与单链DNA作用时,配合物能键合到DNA碱基所在的疏水区,在与富含dC和dT碱基的序列相结合时,发生显著的能量传递,从而极大的增强了配合物中Eu的发射光谱。配合物结合DNA的化学计量比随序列中dC含量的降低而降低。配合物同样能够与处于DNA疏水区的富含dA和dG序列相结合,这种结合不能够产生能量传递,但使得DNA的紫外-可见光谱出现明显的减色和红移现象。此外,这一配合物还能够诱导单链DNApoly(dA)及p01y(rA)产生自身的二级结构,形成双链结构。这为进一步认识斓系离子的生物学效应奠定了基础,斓系氨基酸配合物可以诱导单链poly(dA)及poly(rA)形成自身结构尚无文献报道。3.Eu一AsP配合物能够选择性的稳定非B一构象的Poly(dA)Poly(dT),而使B一构象的印oly(dAdT)]2和[Poly(dGdC)]2变得不稳定。如在1:2比例时,该配合物可使Poly(dA)Polv(dT)的融化温度提高4℃,而使印oly(dAdT)}2的融化温度降低6℃,[Poly(dGdC)]2则出现了两个转变温度。进一步的圆二色实验结果充分表明Eu一Asp配合物对于富含Poly(dA)Poly(dT)和[Poly(dAdT)]2的双链DNA没有构象上的改变,而对于[Poly(dGdC)]2的双链DNA则产生了显著的构象上的改变,很有可能正是这一改变使得[Poly(dGdC)]2变得极其的不稳定。配合物对[Poly(dGdC)]2的这种不稳定影响随着配合物浓度的逐步升高而越来越明显。变温实验结果清楚的表明,在37℃时,Eu-AsP使[Poly(dGdC)JZ发生了构象转化,并且这种转化是可逆的。4.Tb-Cys配合物与单链(除了poly(dA))和双链DNA都能发生能量传递,从而使得配合物的荧光显著增强。不同的DNA表现出不同的增强效果,表明TbCys配合物对DNA的序列存在选择性,单链要强于双链,富含Poly(dAdG)的序列增强效果最好。单链和双链能量传递的差异表明了配合物能够区分DNA的单链和双链,配合物在与单链作用时结合更强。TbCys配合物在与DNA作用时存在不同的结合位点,而且单链和双链的结合位点明显不同。TbCys配合物能够引起富含dC和dT的单链DNA发生减色效应,而能够引起富含poly(dA)、poly(dAdG)的单链DNA和富含poly(dA)poly(dT)、[Poly(dAdT)]2和[poly(dGdC)]2的双链DNA发生明显的红移。此外,这一配合物同样能够影响双链DNA的稳定性,使得富含poly(dA)Poly(dT)序列变得稳定,而使得富含印oly(dAdT)]2和富含印oly(dGdC)]2的序列变得不稳定。这些结果都表明了配合物对DNA存在选择性。比较不同配合物的差别后能够发现DNA对于不同的配合物同样具有选II择性,这种选择性能够用来区分配合物。一这些钢系氨基酸配合物由于选择了天然的氨基酸作为配体,从而大大的降低了对人体的毒性,进一步表现出的对不同的DNA序列的选择型则使其有望成为新型的抗癌诊疗试剂。

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本文合成了四氢糠基环戊二烯, 并以其为配体合成了四氢糠基环戊二烯基钠盐及四氢糠基环戊二烯基稀土配合物,用元素分析,红外光谱,质谱,核磁共振谱,光电子能谱进行了表征,用X-射线衍射法测定了四氢糠基环戊二烯基钠和四氢糠基环戊二烯基镝和镱的晶体结构。

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本文用二维核磁共振、富利叶变换拉曼光谱和差示扫描量热等方法研究了:1)稀土离子与柠檬酸配体的溶液配位行为,并用顺磁位移试剂的方法计算了该条件下的配合物形成稳定常数;2)稀土离子及其配合物与不同种类的磷脂分子的作用;3)二氧化硅和柠檬酸铝与DPPC脂质体的作用。

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The crystallographic and intrinsic magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) have been investigated. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions, mainly along the a- and b-axis rather than along the c-axis, are observed for all the compounds upon hydrogenation. Hydrogenation leads to an increase in Curie temperature. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and Tb(3)Fc(27.0)Cr(2.0)H(2.8), and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2 Abnormal crystallographic and magnetic properties of Ce3Fe29-xTxHy suggest that the Ce ion is non-triply ionized.