Design of 3d-4f molecular squares through the [Fe{(HB(pz)3)}(CN)3]- metalloligand

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dc.creatorMaria-Gabriela Alexandru
dc.creatorDiana Beatrice Visinescu
dc.creatorSergiu Shova
dc.creatorWillian Xerxes Coelho Oliveira
dc.creatorFrancesc Lloret
dc.creatorMiguel Julve
dc.date.accessioned2023-02-02T17:33:08Z
dc.date.accessioned2025-09-09T01:09:06Z
dc.date.available2023-02-02T17:33:08Z
dc.date.issued2018
dc.description.sponsorshipOutra Agência
dc.identifier.doihttps://doi.org/10.1039/C8DT00895G
dc.identifier.issn1477-9234
dc.identifier.urihttps://hdl.handle.net/1843/49480
dc.languageeng
dc.publisherUniversidade Federal de Minas Gerais
dc.relation.ispartofDalton Transactions
dc.rightsAcesso Restrito
dc.subjectQuímica supramolecular
dc.subjectCristalografia de raio X
dc.subjectMagnetismo
dc.subjectCompostos metálicos
dc.subjectEstrutura molecular
dc.subjectPropriedades magnéticas
dc.subject.otherCyanide
dc.subject.otherHeterometallic complexes
dc.subject.otherCyanido-bridged
dc.subject.otherSynthesis
dc.subject.otherCrystal structure
dc.titleDesign of 3d-4f molecular squares through the [Fe{(HB(pz)3)}(CN)3]- metalloligand
dc.typeArtigo de periódico
local.citation.epage6017
local.citation.issue17
local.citation.spage6005
local.citation.volume47
local.description.resumoA new series of {FeIII2LnIII2} heterobimetallic squares of general formula [FeIII{HB(pz)3}(CN)(μ-CN)2Ln(pyim)x(NO3)2(H2O)y]2·zH2O [Ln = La (1), Gd (2), Tb (3) and Dy (4); {HB(pz)3}− = hydrotris(pyrazolyl)borate and pyim = 2-(1H-imidazol-2-yl)pyridine; x = 2, y = 0 (1), x = y = 1 (2–4) and z = 10 (1), 6 (2), 2.76 (3), 4 (4)] were synthesized by reacting the low-spin [FeIII{HB(pz)3}(CN)3]− complex anion with the preformed [LnIII(pyim)x(NO3)2(H2O)y]+ complex cation [formed in situ by mixing the lanthanide(III) salt and the pyim ligand]. Single-crystal X-ray diffraction shows that 1–4 crystallize in the P[1 with combining macron] triclinic space group, 2–4 being isomorphous. In all cases, the structure comprises neutral cyanido-bridged {FeIII2LnIII2} molecular squares in which two [FeIII{HB(pz)3}(CN)3]− units act as bis-monodentate ligands towards two [LnIII(pyim)x(NO3)2(H2O)y]+ moieties through two of the three cyanide groups. The iron(III) and lanthanide(III) cations regularly alternate in the corners of the square and the edges are defined by the cyanide bridges. Each iron(III) ion in 1–4 is six-coordinate in a distorted octahedral surrounding with a tridentate tris(pyrazolyl)borate ligand and three cyanide groups in an approximately C3v symmetry. The lanthanum(III) ion in 1 is ten-coordinate in a rare distorted sphenocorona environment, while the lanthanide(III) ions in 2–4 are all nine-coordinate with a muffin-like geometry. The values of the FeIII⋯LnIII distances across the cyanide bridges are 5.579(1) and 5.687(1) Å (1), 5.4695(20) and 5.4781(29) Å (2), 5.4550(12) and 5.4464(14) Å (3), 5.4463(10) and 5.4478(12) Å (4). The tetranuclear units in 1–4 are further interconnected through hydrogen bonds, π–π stacking and very weak C–H⋯π type interactions leading to supramolecular three-dimensional networks with different topologies. Solid-state direct-current magnetic susceptibility analyses in the temperature range 1.9–300 K reveal the occurrence of weak intra- and intermolecular antiferromagnetic interactions in 1 [JFeFe′ = −2.32(3) cm−1, gFe = 2.198(4), θ = −0.650(7) K and χTIP = 266(5) × 10−6 cm3 mol−1, the Hamiltonian being defined as H = −JFeFe′SFeSFe′ + gβH(SFe + SFe′)] and 2 [JFeFe′ = −2.06(3) cm−1, JFeGd = −0.210(4) cm−1, gFe = 2.23(1), gGd = 2.0 (fixed), θ = −0.450(5) K and χTIP = 280(5) × 10−6 cm3 mol−1]. The coexistence of the spin–orbit coupling of the low-spin iron(III) and lanthanide(III) ions [TbIII (3) and DyIII (4)], together with the ligand field effects, masked the visualization of the possible magnetic interactions in 3 and 4. The small antiferromagnetic couplings in 1 and 2 are in line with previously reported weak antiferromagnetic interactions for these couples of ions through single cyanide bridges.
local.identifier.orcidhttps://orcid.org/0000-0001-8640-5807
local.identifier.orcidhttps://orcid.org/0000-0003-3800-0674
local.identifier.orcidhttps://orcid.org/0000-0002-1222-4373
local.identifier.orcidhttps://orcid.org/0000-0003-0722-5352
local.identifier.orcidhttps://orcid.org/0000-0003-2959-0879
local.identifier.orcidhttps://orcid.org/0000-0001-9006-8268
local.publisher.countryBrasil
local.publisher.departmentICX - DEPARTAMENTO DE QUÍMICA
local.publisher.initialsUFMG
local.url.externahttps://pubs.rsc.org/en/content/articlelanding/2018/DT/C8DT00895G

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