Neutron diffraction study of the crystal structure of rare-earth and yttrium anhydrous deuterated formates

Bolotovsky, Robert; Bulkin, A.P.; Krutov, G.A.; Kudryashev, V.A.; Trunov, V. A.; Ul’yanov, V.A.; Antson, Olli; Hiismäki, Pekka; Pöyry, Heikki; Tiitta, A.; Loshmanov, A. A.; Furmanova, N. G.

doi:10.1016/0038-1098(90)90081-l

Cited by 20 publications

(20 citation statements)

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“…Chemical substitution of formate for longer bridging ligands may allow even more extreme J /J ⊥ values to be realised, presumably stabilising 1D behaviour over a larger temperature range. There is scope too for substitution at the Tb 3+ site, since the lanthanide formates are isostructural [31]. Because Gd(HCOO) 3 is known to show AFM coupling within chains, the solid solution Gd 1−x Tb x (HCOO) 3 [25] may provide an attractive entry point for the realisation of random-chain 1D magnets [48].…”

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One-dimensional magnetic order in the metal-organic framework Tb(HCOO)3

et al. 2016

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A combination of variable-temperature neutron scattering, reverse Monte Carlo analysis and direct Monte Carlo simulation is used to characterise the emergence of magnetic order in the metal-organic framework (MOF) Tb(HCOO)3 over the temperature range 100 K to 1.6 K = TN. We show that the magnetic transition at TN involves one-dimensional ferromagnetic ordering to a partially-ordered state related to the triangular Ising antiferromagnet. In this phase, the direction of magnetisation of ferromagnetic chains tends to alternate between neighbouring chains but this alternation is frustrated and is not itself ordered. In neutron scattering measurements this partial order gives rise to Bragg-like peaks, which cannot be interpreted using conventional magnetic crystallography without resort to unphysical spin models. The existence of low-dimensional magnetic order in Tb(HCOO)3 is stabilised by the contrasting strength of inter-and intra-chain magnetic coupling, itself a consequence of the underlying MOF architecture. Our results demonstrate how MOFs may provide an attractive if as yet under-explored platform for the realisation and investigation of low-dimensional physics.Low-dimensional magnets have long provided an important playground for the discovery and exploitation of unconventional physics [1]-from the earliest studies of soliton excitations in CsNiF 3 [2-4] to contemporary research into quantum information transport in spin-chain compounds [5]. The sensitivity of low-dimensional spin systems to small perturbations results in a rich diversity of phase transitions and complex ordering phenomena. By way of example, the Ising spin-chain compound Ca 3 Co 2 O 6 exhibits a variety of equilibrium and non-equilibrium states [6][7][8], characterised by e.g. long-wavelength incommensurate spin density modulations and field-induced magnetisation plateaux reminiscent of Hofstadter fractalisation [9,10]. In the field of low-dimensional magnetism, arguably the strongest scientific interest from both experimental and theoretical perspectives has always been in the limit of strict 1D order [11][12][13][14][15][16]. Yet even in canonical systems such as Ca 3 Co 2 O 6 the divergence of correlation lengths along 1D spin chains is always accompanied by full 3D magnetic order [8,17]. So the realisation and experimental characterisation of genuine partially-ordered low-dimensional spin states remain an important challenge in the field.It was in this context that we chose to study magnetic order in terbium(III) formate, Tb(HCOO) 3 . In metal-organic frameworks (MOFs) such as Tb(HCOO) 3 , magneticallyactive transition-metal or rare-earth ions are connected via organic ligands to form extended 3D framework structures. Because organic ligands can support superexchange interactions that span a broad energy range, and because framework design allows controlled incorporation of low-dimensional structural motifs (e.g. chains, ladders, layers), MOFs are natural candidate hosts for low-dimensional magnetism [18]. Indeed the magnetic response of...

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“…Under ambient conditions, Tb(HCOO) 3 crystallises in the rhombohedral space group R3m [25,31,32]. All Tb • -a geometry that favours ferromagnetic coupling and provides a uniaxial crystal field at the Tb 3+ site (point symmetry 3m) [25].…”

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One-dimensional magnetic order in the metal-organic framework Tb(HCOO)3

et al. 2016

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“…The title crystal structure, is isotypic with numerous lanthanide formates, like those of La, Ce, Tb and Tm [5]. Unit cell data have been reported previously for [Nd(HCO 2 ) 3 ] n [6], although the compound was described in that case as afractional hydrate and atomic coordinates were not determined.…”

Section: Discussionmentioning

confidence: 94%

Crystal structure of neodymium(III) formate, Nd(HCO2)3

Deng¹,

Zhang²,

Xiao³

et al. 2009

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialBiphenyl-3,3',4,4'-tetracarboxylic acid (0.033 g, 0.1 mmol), Nd(NO 3 ) 3 · 6H 2 O(0.0876 g, 0.2 mmol), NaOH (0.4 mmol, 0.016 g), DMF (N,N-dimethylformamide; 1m L), H 2 O( 6m L), and HNO 3 (0.5 mL, 0.75 MinH2O) were added respectively to a15 mL Teflon-lined steel autoclave, which was sealed and heated to 443K for 3d ays and then cooled to room temperature. Perfect pink block crystals were collected. Chemical analysis -found: C, 12.85 %; H, 1.12 %; calculated for C 3H3NdO6:C,12.90 %, H, 1.08 %. The synthesis of the title compound is out of the expectation of our original purpose. The ligand in the complex is af ormate, which was not directly introduced as one of the starting reaction materials. The starting materials biphenyl-3,3',4,4'-tetracarboxylic acid do not take part in the coordination. The synthetic procedure involves DMF and H 2 Oassolvents, and we think the formate group comes from DMF. Similar situation also occurred in other systems [1][2][3], and it has long been known that DMF can be hydrolyzed to formate and DMA (dimethylamine) and that the rate of this process increases at high temperature and pressure [4]. DiscussionThe title crystal structure, is isotypic with numerous lanthanide formates, like those of La, Ce, Tb and Tm [5]. Unit cell data have been reported previously for [Nd(HCO 2 ) 3 ] n [6], although the compound was described in that case as afractional hydrate and atomic coordinates were not determined. The title compound is a 3D neutral framework composed of Nd(III) ions and formate anions in a1:3ratio. The asymmetric unit contains 1/3 neodymium(III) cation and one formate HCO 2 − anion. The Nd ion lies on asite of 3m symmetry and is coordinated by nine Oatoms from nine HCO 2 − anions, which lie on mirror planes. The coordinating oxygen atoms of the formate ligand differ with respect to their linkage. O1 forms m 2-bridges between neighbouring neodymium centres, while O2 is monocoordinating. Each Catom makes three C−O−Nd linkages through one m 2-bridging Oatom (O1) and one m 1 -bound Oatom (O2). Three Nd ions and three HCO 2− anions are connected, forming six-membered rings, which are connected by further HCO 2− anions, generating a3Dframework. The distance between adjacent Nd ions is 4.0588(8) Å.

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“…In Ref. [1], Bolotovski et al, obtained the bond distance variations in the RE(DCOO) 3 (RE = La, Ce, Tb, Y and Tm) compounds. According to Table 2 of Ref.…”

Section: Resultsmentioning

confidence: 99%

“…According to Table 2 of Ref. [1], the distances C-O(1), C-O(2) and C-D, related to the DCOO internal modes, are not significantly altered when one proceeds from Tm (V = 417.5 Å 3 )…”

Section: Resultsmentioning

confidence: 99%

Vibrational modes of rare‐earth formates

Silva

Moura

Ayala

et al. 2009

J Raman Spectroscopy

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In this work we investigate the room-temperature Raman spectra of several rare-earth [RE(HCOO) 3 ; RE = La, Pr, Nd, Gd, Tb and Y] formates. Polarized measurements were carried out for La(HCOO) 3 yielding the observation of most of the Ramanactive phonons predicted by group theory analysis. The respective assignment is given based on the formate vibrations and correlations with previous results in other RE(HCOO) 3 systems. The wavenumber 'softening' observed when RE goes from Y to La is accounted for the lattice expansion.

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Neutron diffraction study of the crystal structure of rare-earth and yttrium anhydrous deuterated formates

Cited by 20 publications

References 10 publications

One-dimensional magnetic order in the metal-organic framework Tb(HCOO)3

One-dimensional magnetic order in the metal-organic framework Tb(HCOO)3

Crystal structure of neodymium(III) formate, Nd(HCO2)3

Vibrational modes of rare‐earth formates

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