Gd Derivative Research Articles

Synthesis, structure, magnetic properties of one‐dimensional Cu‐Ln chains linked by a nitronyl nitroxide radical with two pyridyl groups

AbstractTwo new Cu−Ln 1D coordination chains with formula [Ln(hfac)3Cu(hfac)2 (NIT‐3Py‐5‐3Py)(H2O)]n (LnIII=Gd 1, Dy 2; hfac=hexafluoroacetylacetonate, NIT‐3Py‐5‐3Py=2‐(5‐(3‐pyridyl)‐3‐pyridyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide) were successfully constructed by means of a new nitronyl nitroxide radical ligand containing two pyridine groups. In these two complexes, the radical ligand binds two CuII ions through its two pyridine groups to produce 1D chain while the aminoxyl moiety of the radical is bound to a Ln (III) ion. Direct‐current magnetic susceptibility investigations indicate that ferromagnetic exchanges are dominant and magnetic susceptibility data of Gd derivative are analyzed using a magnetic model, indicating that Cu‐NO coupling through pyridine group and Gd‐NO direct exchange are ferromagnetic interactions. There is no magnetic relaxation behavior for Dy analogue.

Structural and magnetic characterization of tetranuclear [Ni(II)2Ln(III)2] complexes bearing tetra-branched Schiff base ligands

A series of tetranuclear [Ni(II)2Ln(III)2] complexes of general formula [Ni2Ln2(L)(H2O)9(OH)4Cl]∙3H2O∙Cl (1, 2, 5) (Ln = Dy (1), Tb (2), Ho (5)) and [Ni2Ln2(L)(H2O)12Cl] ∙3H2O∙5Cl (3, 4, 6, 7) (Ln = Gd (3), Sm (4), Nd (6), Pr (7)); H4L = N,N’,N’’,N’’’-tetra(3-methoxysalicylidene)-pentaerythritol) have been synthesized. The molecular structures and magnetic properties of 1–7 are reported. Structural analysis indicated that this family of clusters consists of a tetranuclear [Ni(II)2Ln(III)2] core, supported by a tetrapodal Schiff base ligand. Both Ni(II) ions adopt a distorted octahedral coordination environment, whilst the two terminal Ln(III) ions exhibit distorted tricapped trigonal prismatic geometries and are coordinated by eight or nine oxygen donor atoms. Magnetic measurements revealed that the Dy derivative of complex 1 displays typical d single-molecule magnet behaviour with the presence of slow magnetic relaxation. By contrast, complexes 2–7, no obvious SMM behaviour was exhibited, however for the Gd derivative 3, a significant magnetocaloric effect was observed.

Multifunctional properties of {CuLn} systems involving nitrogen-rich nitronyl nitroxide: single-molecule magnet behavior, luminescence, magnetocaloric effects and heat capacity.

A series of nitrogen-rich nitronyl nitroxide radical PPNIT (1)-based (PPNIT = 2-(1-(pyrazin-2-yl)-1H-pyrazole)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) 3d-4f ring-shaped tetranuclear clusters [Ln2Cu2(hfac)10(PPNIT)2(H2O)2]·CHCl3 (LnIII = Gd 2, Tb 3, Dy 4; hfac = hexafiuoroacetylacetonate) with multifunctional properties were isolated. The magnetic behavior, luminescence and heat capacity of the 3d-4f complexes were investigated, displaying interesting multiple properties of the molecular materials. The Gd derivative shows a magnetocaloric effect with the maximum entropy change (-ΔSm) of 15.3 J kg-1 K-1 at 2 K for ΔH = 70 kOe. The Tb cluster exhibits spin glass behavior and the characteristic fluorescence emission of the TbIII ion, while the Dy cluster exhibits SMM behaviour, and the heat capacity has been investigated. Notably, in nitronyl nitroxide radical-metal systems, the investigation of diverse properties is still scarce so far. This work can pave the way towards the synthesis of multifunctional materials that combine SMM behavior, and optical or/and thermodynamic properties.

Designing Multicoordinating Nitronyl Nitroxide Radical Toward Multinuclear Lanthanide Aggregates.

Profiting from a multicoordinating nitronyl nitroxide radical, i.e. a functionalized nitronyl nitroxide biradical ligand, a family of novel tetranuclear lanthanide complexes, formulated as [RE4(hfac)12(NITPhO-3Pybis)2] (RE = Gd 1, Tb 2, Dy 3, Ho 4, and Y 5; NITPhO-3Pybis = 5-(3-pyridinyloxy)-1,3-bis(1'-oxyl-3'-oxido-4',4',5',5'-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene; hfac = hexafluoroacetylacetonate) were successfully constructed and characterized. In these complexes, the designed functionalized nitronyl nitroxide biradical ligand functions as the chelating and/or bridging ligand to bind the lanthanide ions, resulting in tetranuclear octa-spin lanthanide complexes with a circle-shaped arrangement. Direct-current magnetic data show that antiferromagnetic interaction dominates in the Gd derivative, while ferromagnetic coupling plays a leading role in complex Y, in which the relevant magnetic exchange parameters were obtained through applicable magnetic models. Dynamic magnetic studies of Tb and Dy analogues exhibit apparent frequency-dependent out-of-phase signals, which are typical features for slow magnetic relaxation behavior. The values of Ueff and τ0 were obtained as follows: Ueff = 10.5 K and τ0 = 6.6 × 10-7 s for the Tb complex and Ueff = 5.2 K and τ0 = 2.5 × 10-6 s for the Dy compound. Intriguingly, the butterfly shaped hysteresis loop is found for the Tb analogue. Guided by fluorescence spectra, the representative peaks are identified for the Tb derivative.

Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains.

The rational design of molecular chains made of 4f ions and substituted 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical is presented. The reaction of Ln(hfac)3·2H2O (hfac- = hexafluoroacetylacetonate) and the 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO-CN) radical affords air- and moisture-stable isostructural molecular chains of the formula [Ln(hfac)3TEMPO-CN] n for Ln = GdIII and TbIII, whereas zero-dimensional complexes of the formula [Dy(hfac)3(TEMPO-CN)2][Dy(hfac)3(H2O)2]2 are obtained for Ln = DyIII. To the best of our knowledge, the Gd derivative, Gd-TEMPO-CN, shows one of the strongest antiferromagnetic (AF) couplings for Gd-radical pairs ever reported with JGd-rad/ kB = -21.18 K, 14.72 cm-1 ( H = - JSrad SGd spin Hamiltonian convention). The TbIII derivative, Tb-TEMPO-CN, also shows strong Tb-radical AF coupling, which has been rationalized using the ab initio CASSCF approach ( JTb-rad = -23.02 K, -16.7 cm-1) and confirmed by luminescence measurements. Tb-TEMPO-CN shows remarkable properties for a Tb-radical-based single-molecule magnet ( Ueff = 69.3 ± 1 K; τ0 = 1.3 × 10-7 s) and two different relaxation processes triggered by interchain magnetic coupling.

Two-dimensional Co-Ln networks bridged by phenyl pyrimidyl substituted nitronyl nitroxides: structural and magnetic properties.

Two-dimensional hetero-tri-spin 2p-3d-4f coordination polymers involving Co(ii) and Ln(iii) ions assembled with a polydentate paramagnetic nitronyl nitroxide ligand are reported. [Ln(hfac)3{Co(hfac)2}2(NITPhPyrim)2] (LnIII = Gd 1, Tb 2; hfac = hexafluoroacetylacetonate, NITPhPyrim = 2-[4-(5-pyrimidyl)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) consists of a two-dimensional network in which the NITPhPyrim ligand is coordinated to the metal ions by means of its pyrimidine and aminoxyl (NO) groups. In the layer, the Tb center interacts with two NO groups from two different radical ligands, and each pyrimidine connects two Co(hfac)2 units through its two nitrogen atoms to form one-dimensional Co(ii) arrays. The magnetic behavior of the two compounds results from concomitant ferro- and antiferromagnetic interactions between the spin carriers and the spin-orbit effect from Co(ii) as revealed by modeling performed for the Gd(iii) derivative.

Self-assembly of rare octanuclear quad(double-stranded) cluster helicates showing slow magnetic relaxation and the magnetocaloric effect

Four rare structurally novel octanuclear quad(double-strands) cluster helicates containing Ln8 polyhedron cores have been synthesized. Magnetic studies show that the Gd derivative exhibits the magnetocaloric effect and the Dy derivative shows slow magnetic relaxation under zero dc field.

Fluorinated mercaptobenzothiazolates of lanthanides: Synthesis, structure and photoluminescence

In search of new fully fluorinated ligands which effectively sensitized the lanthanide luminescence the 4,5,6,7-tetrafluoro-1,3-benzothiazol-2(3Н)-thione (HmbtF) was proposed. Based on this ligand a set of new complexes LnL3(THF)2 (Ln1) (Ln = Nd, Gd, Tb, Dy, Er, Yb) was synthesized and their luminescence were studied. The structure of the compounds was established with an example of Gd derivative. The triplet state energy of mbtF was found to be 21500 cm−1 that enables the resonant energy transfer to Dy3+, Tb3+, Nd3+ and Er3+ ions and stipulates metal-centered emission of some complexes. In case of Yb1 the observed luminescence of Yb3+ ion probably occurs due to the non-resonant energy transfer.

Syntheses, Structures, Luminescence, and Magnetic Properties of a Series of Novel Coordination Polymers Constructed by Nanosized [Ln8Fe4] Rings

A total of five three-dimensional Ln-Fe coordination polymers (CPs) [(CH3)2NH][(CH3)2NH2][Ln2Fe(SO4)4(L)]·3H2O (Ln = Eu, 1; Dy, 2; Gd, 3; Sm, 4; Er, 5; H2L = tartaric acid) have been successfully synthesized under solvothermal conditions and characterized by infrared spectroscopy, thermogravimetric analysis, elemental analyses, luminescence, and magnetic properties. Structural analysis indicates that the frameworks of 1–5 are constructed from novel [Ln8Fe4] rings. In the strcutures of 1–5, LnIII and FeIII ions interconnect through O donors of sulfate anions to generate a one-dimensional chain, and the adjacent chains are joined together by ligand [L]2– to form a two-dimensional zonary plane, which is further bridged by ligand [L]2– to give a new topology and named as “Xhd1”. Magnetic properties of 2 and 3 were investigated using variable temperature magnetic susceptibility, and weak ferromagnetic exchange between the FeIII and LnIII ions has been established for the Gd derivative. Meanwhile, we also studi...

Towards phasing using high X-ray intensity.

X-ray free-electron lasers (XFELs) show great promise for macromolecular structure determination from sub-micrometre-sized crystals, using the emerging method of serial femtosecond crystallography. The extreme brightness of the XFEL radiation can multiply ionize most, if not all, atoms in a protein, causing their scattering factors to change during the pulse, with a preferential 'bleaching' of heavy atoms. This paper investigates the effects of electronic damage on experimental data collected from a Gd derivative of lysozyme microcrystals at different X-ray intensities, and the degree of ionization of Gd atoms is quantified from phased difference Fourier maps. A pattern sorting scheme is proposed to maximize the ionization contrast and the way in which the local electronic damage can be used for a new experimental phasing method is discussed.

Syntheses, crystal structures, and magnetic properties of a series of Fe2Ln complexes

A family of phenoxo-bridged heterometallic Schiff base trinuclear complexes, [Fe2LnL2(C3H7COO)(H2O)]·CH3OH·CH3CN·H2O (Ln = Sm, 1; Gd, 2; Tb, 3; Dy, 4) is reported. Those complexes were afforded by “one-pot” reaction of a polydentate Schiff base ligand 2-hydroxy-3-methoxy-phenylsalicylaldimine (H2L) with Fe(NO3)3·9H2O, Ln(NO3)3·6H2O and sodium butyrate (C3H7COONa) in a mixture of methanol and acetonitrile in the presence of triethylamine as a base. Single-crystal X-ray diffraction analysis reveals that the structures of the four complexes are isomorphic. In each complex, two anionic [FeL2]− units coordinate to the central lanthanide ion as a tetradentate ligand using its four phenoxo oxygens, forming a two-blade propeller-like molecular shape. Magnetic properties of 1–4 were investigated using variable temperature magnetic susceptibility, and weak ferromagnetic exchange between the FeIII and LnIII ions has been established for the Gd derivative. The Tb and Dy complexes show no evidence of slow relaxation behavior above 2.0 K.

Nitronyl nitroxide based 2p-3d-4f chains with the magnetocaloric effect and slow magnetic relaxation.

Four new nitronyl nitroxide radical based hetero-tri-spin one-dimensional compounds, namely [{Ln(hfac)3}3{Cu(hfac)2}{NIT-Ph(OMe)2}4]n (Ln = Gd (1), Tb (2), Dy (3), Er (4); hfac = hexafluoroacetylacetonate; NIT-Ph(OMe)2 = 2-(2',4'-dimethoxyphenyl)-4,4,5,5-tetramethyl-imidazolyl-1-oxyl-3-oxide) have been successfully prepared. Single crystal X-ray crystallographic analysis reveals that complexes 1-4 possess a 1D chain structure with a repeating [Cu-Rad-Ln-Rad-Ln-Rad-Ln-Rad] moiety in which Ln(hfac)3 and Cu(hfac)2 units are bridged by nitronyl nitroxide radicals through the NO groups. DC magnetic studies found that ferromagnetic interactions between metals and the coordinated NO groups are active in all four compounds. The Tb derivative displays frequency dependent ac magnetic susceptibilities, indicating slow magnetic relaxation behavior. The Gd complex shows an important cryogenic magnetocaloric effect with the entropy change (-ΔSm) of 13.5 J kg(-1) K(-1) at 2 K and a magnetic field of 7 T, representing the first example of Gd-radical molecular species exhibiting the magnetocaloric effect.

Crystal Packing Effects on the Magnetic Slow Relaxation of Tb(III)-Nitronyl Nitroxide Radical Cyclic Dinuclear Clusters

Four lanthanide-based nitronyl nitroxide radical cyclic molecular clusters of formula [Ln(hfac)3(NITPhPO(OEt)2)]2 (Ln(III) = Gd (1), Tb (2A and 2B), and Dy (3) and NITPhPO(OEt)2 = 4'-[2-(1-oxyl-3-4,4,5,5-tetramethylimidazoline)phenyl]diethoxylphosphine oxide) have been synthesized. Their X-ray structures have been solved and highlight two different crystal packings. For the particular case of the Tb(III) derivative, both of them can be obtained. In 2A, the molecules are well-isolated, while 2B shows short contacts between N-O radical groups. Static magnetic studies on the Gd(III) derivative (1) demonstrate that lanthanides and radicals are ferromagnetically coupled (J = 3.46 ± 0.04 cm(-1)). Dynamic magnetic studies show that both compounds 2A and 2B exhibit single molecule magnet behavior. A comparison of their magnetic behaviors highlights that the crystal packing has a crucial influence on the temperature range in which the SMM behavior is observed. In the case of the well-insulated Tb(III)-based derivative (2A), the SMM behavior is observed at higher temperatures and lower frequencies than for the one that presents close-packing between the molecules (2B). Comparisons are then possible only under an applied external magnetic field (0.2 T) with Δ = 27.5(6) and 21.0(5) K and τ0 = 2.64(25) × 10(-9) and 1.76(20) × 10(-9) s for 2A and 2B, respectively.

Amine-Templated Polymeric Lanthanide Formates: Synthesis, Characterization, and Applications in Luminescence and Magnetism

The novel polymeric formates of general formula [(Fmd)Ln(III)(HCOO)(4)](∞) (Fmd(+) = NH(2)-CH(+)-NH(2); Ln = Eu (1), Gd (2), Tb (3), Dy (4)] were synthesized through solvothermal methods in formamide solutions. The compounds are isotructural; they crystallize in the orthorhombic C222(1) chiral space group. The coordination geometry at the metal centers is square antiprismatic (coordination number eight), with each formate ligand bridging adjacent lanthanide ions. The overall negative three-dimensional (3D) framework charge is balanced by the formamidinium cations sitting inside the channels along the a axis, forming extensive N-H···O hydrogen bonding with the surrounding cage. All the compounds have been characterized through single-crystal/powder X-ray diffraction, IR spectroscopy, and TG-MS analysis. Finally, their luminescence and magnetic properties have been assessed, leading to remarkable emission intensities, especially for the Tb(III) compound (Φ = 0.83), with corresponding lifetime decays in the micro (Dy) and millisecond (Tb, Eu) time scale. A weak but sizable antiferromagnetic interaction has been observed for the Gd(III) derivative.

Co–Ln Mixed-Metal Phosphonate Grids and Cages as Molecular Magnetic Refrigerants

The synthesis, structures, and magnetic properties of six families of cobalt-lanthanide mixed-metal phosphonate complexes are reported in this Article. These six families can be divided into two structural types: grids, where the metal centers lie in a single plane, and cages. The grids include [4 × 3] {Co(8)Ln(4)}, [3 × 3] {Co(4)Ln(6)}, and [2 × 2] {Co(4)Ln(2)} families and a [4 × 4] {Co(8)Ln(8)} family where the central 2 × 2 square is rotated with respect to the external square. The cages include {Co(6)Ln(8)} and {Co(8)Ln(2)} families. Magnetic studies have been performed for these compounds, and for each family, the maximum magnetocaloric effect (MCE) has been observed for the Ln = Gd derivative, with a smaller MCE for the compounds containing magnetically anisotropic 4f-ions. The resulting entropy changes of the gadolinium derivatives are (for 3 K and 7 T) 11.8 J kg(-1) K(-1) for {Co(8)Gd(2)}; 20.0 J kg(-1) K(-1) for {Co(4)Gd(2)}; 21.1 J kg(-1) K(-1) for {Co(8)Gd(4)}; 21.4 J kg(-1) K(-1) for {Co(8)Gd(8)}; 23.6 J kg(-1) K(-1) for {Co(4)Gd(6)}; and 28.6 J kg(-1) K(-1) for {Co(6)Gd(8)}, from which we can see these values are proportional to the percentage of the gadolinium in the core.

Single‐Molecule Magnet Behaviour in a Tetrathiafulvalene‐Based Electroactive Antiferromagnetically Coupled Dinuclear Dysprosium(III) Complex

The reactions between the [Ln(tta)(3)]·2H(2)O precursors (tta(-)=2-thenoyltrifluoroacetonate anion) and the tetrathiafulvalene-3-pyridine-N-oxide ligands (L(1)) lead to dinuclear complexes of formula [{Ln(tta)(3)(L(1))}(2)]·xCH(2)Cl(2) (x=0.5 for Ln=Dy(III) (1) and x=0 for Ln=Gd(III) (2)). The crystal structure reveals that two {Ln(tta)(3)} moieties are bridged by two donors through the nitroxide groups. The Dy(III) centre adopts a distorted square antiprismatic oxygenated polyhedron structure. The antiferromagnetic nature of the exchange interaction between the two Dy(III) ions has been determined by two methods: 1) an empirical method using the [Dy(hfac)(3)(L(2))(2)] mononuclear complex as a model (3) (hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate anion, L(2)=tetrathiafulvaleneamido-2-pyridine-N-oxide ligand), and 2) assuming an Ising model for the Dy(III) ion giving an exchange energy of -2.30 cm(-1), g=19.2 in the temperature range of 2-10 K. The antiferromagnetic interactions have been confirmed by a quantitative determination of J for the isotropic Gd(III) derivative (J=-0.031 cm(-1), g=2.003). Compound 1 displays a slow magnetisation relaxation without applied external magnetic fields. Alternating current susceptibility shows a thermally activated behaviour with pre-exponential factors of 5.48(4)×10(-7) s and an energy barrier of 87(1) K. The application of an external field of 1.6 kOe compensates the antiferromagnetic interactions and opens a new quantum tunnelling path.

Synthesis, structure and magnetic properties of a novel family of heterometallic nonanuclear NaI2MnIII6LnIII (Ln = Eu, Gd, Tb, Dy) complexes

The structures and magnetic properties of four isomorphous nonanuclear heterometallic complexes [Na(2){Mn(3)(III)(μ(3)-O(2-))}(2)Ln(III)(hmmp)(6)(O(2)CPh)(4)(N(3))(2)]OH·0.5 CH(3)CN·1.5H(2)O are reported, where Ln(III) = Eu (1), Gd (2), Tb (3) and Dy (4), H(2)hmmp = 2-[(2-hydroxyethylimino)methyl]-6-methoxyphenol. Complexes 1-4 were prepared by the reactions of hmmpH(2) with a manganese salt and the respective lanthanide salt together with NaO(2)CPh and NaN(3). Single-crystal X-ray diffraction analyses reveal that the six Mn(III) and one Ln(III) metal topology in the aggregate can be described as a bitetrahedron. The two peripheral [Mn(III)(3)(μ(3)-O(2-))](7+) triangles are each bonded to a central Ln(III) ion with rare distorted octahedral geometry. The magnetic properties of all the complexes were investigated using variable temperature magnetic susceptibility and both antiferromagnetic and ferromagnetic interactions exist in the [Mn(III)(3)(μ(3)-O(2-))](7+) triangle. Weak ferromagnetic exchange between the Ln(III) and Mn(III) ions has been established for the corresponding Gd derivative. The Gd, Tb and Dy complexes show no evidence of slow relaxation behaviour above 2.0 K.

Smooth transition between SMM and SCM-type slow relaxing dynamics for a 1-D assemblage of {Dy(nitronyl nitroxide)2} units

A model example for size effects on the dynamic susceptibility behavior is provided by the chain compound [{Dy(hfac)(3)NitPhIm(2)}Dy(hfac)(3)] (NitPhIm = 2-[4-(1-imidazole)phenyl]nitronyl nitroxide radical). The Arrhenius plot reveals two relaxation regimes attributed to SMM (Delta = 17.1 K and tau(0) = 17.5 x 10(-6) s) and SCM (Delta = 82.7 K and tau(0) = 8.8 x 10(-8) s) behaviors. The ferromagnetic exchange among the spin carriers has been established for the corresponding Gd derivative.

DNA aptamers developed against a soman derivative cross‐react with the methylphosphonic acid core but not with flanking hydrophobic groups

Twelve rounds of systematic evolution of ligands by exponential enrichment (SELEX) were conducted against a magnetic bead conjugate of the para-aminophenylpinacolylmethylphosphonate (PAPMP) derivative of the organophosphorus (OP) nerve agent soman (GD). The goal was to develop DNA aptamers that could scavenge GD in vivo, thereby reducing or eliminating the toxic effects of this dangerous compound. Aptamers were sequenced and screened in peroxidase-based colorimetric plate assays after rounds 8 and 12 of SELEX. The aptamer candidate sequences exhibiting the highest affinity for the GD derivative from round 8 also reappeared in several clones from round 12. Each of the highest affinity PAPMP-binding aptamers also bound methylphosphonic acid (MPA). In addition, the aptamer with the highest overall affinity for PAPMP carried a sequence motif (TTTAGT) thought to bind MPA based on previously published data (J. Fluoresc 18: 867-876, 2008). This sequence motif was found in several other relatively high affinity PAPMP aptamer candidates as well. In studies with the nerve agent GD, pre-incubation of a large molar excess of aptamer candidates failed to protect human butyrylcholinesterase (BuChE) from inhibition. With the aid of three-dimensional molecular modeling of the GD derivative it appears that a hydrophilic cleft sandwiched between the pinacolyl group and the p-aminophenyl ring might channel nucleotide interactions to the phosphonate portion of the immobilized GD derivative. However, bona fide GD free in solution may be repulsed by the negative phosphate backbone of aptamers and rotate its phosphonate and fluorine moieties away from the aptamer to avoid being bound. Future attempts to develop aptamers to GD might benefit from immobilizing the pinacolyl group of bona fide GD to enhance exposure of the phosphonate and fluorine to the random DNA library.

Effects of large cation size-disorder on the magnetic properties of the rare earth cobaltates, Ln 0.5Ba 0.5CoO 3

Magnetic and electrical properties of Ln 0.5Ba 0.5CoO 3− δ with Ln=Dy and Er have been investigated to examine the effects of large cation size-disorder. While the Dy compound shows the small magnetic anomaly around 290 K just as the Gd derivative, the Er compound is essentially paramagnetic due to the large cation size-disorder. Compositions with the same average A-site cation radii as Dy 0.5Ba 0.5CoO 2.91 and Er 0.5Ba 0.5CoO 2.9, but with smaller size-disorder, show progressive evolution of ferromagnetism and metallic properties with decreasing disorder.