A Cyano-Bridged Cr<sup>III</sup>Co<sup>II</sup> Ferromagnet with a Chiral Nanotubular Structure Constituted of Interlocked Single and Double Helices

Zhang, Yuan‐Zhu; Sato, Osamu

doi:10.1021/ic900224b

Cited by 51 publications

(24 citation statements)

References 30 publications

(27 reference statements)

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“…geometry , . Nevertheless, several examples of linear (H 2 dabph) or macrocyclic ligands (15‐pydienN 3 O 2 , 15‐pydienN 5 , 15‐pyN 3 O 2 , tdmmb, or more recent TODA) (Figure S1) provided seven‐coordinate pentagonal bipyramidal complexes with a pentadentate ligand in the equatorial plane, which show a large easy‐axis magnetic anisotropy ( D < 0) in the case of Fe II and Ni II complexes, and on the other side, a large easy‐plane magnetic anisotropy ( D > 0) in the case of Co II complexes. Slow relaxation of magnetization was observed for [Fe(H 2 dabph)Cl 2 ] and [Fe(H 2 dabph‐NH 2 )Cl 2 ] ( τ 0 = 5 × 10 –9 s and U eff = 53 cm –1 ), for [{Ni(H 2 dabph)} 3 {W(CN) 8 } 2 ] (below the blocking temperature T N = 3.6 K, τ 0 = 1.6 × 10 –9 s, U eff = 30 K), and for many different Co II complexes , , , .…”

Section: Introductionmentioning

confidence: 99%

Structure and Magnetism of Seven‐Coordinate Fe^III, Fe^II, Co^II and Ni^II Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand

et al. 2018

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A heptadentate macrocyclic ligand, H 2 L (3,12,18triaza-6,9-dioxabicyclo[12.3.1]octadeca-1,14,16-triene-3,12-diacetic acid) with two acetate pendant arms, and its complexes [Fe III L]ClO 4 (1), [Fe II L]·H 2 O (2), [Co II L]·H 2 O (3), and [Ni II L]·H 2 O (4) were synthesized. The complexes possess an axially compressed pentagonal bipyramidal geometry with the coordination numbers of 7 for 2 and 3, and 6 + 1 for 4. The magnetic susceptibility measurements revealed magnetic anisotropy for compounds 1-4 expressed by axial zero-field splitting (ZFS) parameters (D = [a] [{Ni(H 2 dabph)} 3 {W(CN) 8 } 2 ] (below the blocking temperature T N = 3.6 K, τ 0 = 1.6 × 10 -9 s, U eff = 30 K), [22] and for many different Co II complexes. [10,18,23,24] Furthermore, the magnetic anisotropy has been tuned by playing with donor/acceptor properties of two axial coligands, as was shown on series of Co II complexes, e.g. [Co(tdmmb)(X) 2 ] 2+/0 , [20] where X = H 2 O, CN -, NCS -, SPh -, with the more pronounced anisotropy for the complex with SPh -(D = 39.7 cm -1 ), or [Co(15-pyN 3 O 2 )X 2 ], [23] where X = Cl -, Brand Iwith the highest D = 41 cm -1 for the dibromido complex, and also on Mn II complexes [Mn(15-pyN 3 O 2 )X], [25] where X = Br -, I -, N 3 -, NCS -, with a small influence of axial coligands on the magnetic anisotropy (|D| < 0.7 cm -1 ).The recent results suggest that also seven-coordinate lanthanide complexes with pentagonal bipyramidal geometry show remarkable properties, [26] concretely a very high magnetization reversal barrier was found for [Dy(OPCy 3 )(H 2 O) 5 ] 3+ , [27] [Dy(tBuPO(NHiPr) 2 ) 2 (H 2 O) 5 ] 3+ , [28] [Dy(bbpen)Cl], and [Dy-(bbpen)Br] [29] with U eff = 543, 735, 708, and 1025 K, respectively.A different approach how to tune desired structural and magnetic properties of complexes can be associated with modification of the original pentadentate macrocycle, e.g. 15-pyN 3 O 2 , with two pendant arms containing different functional groups providing heptadentate ligand and seven-coordinate complexes. Variations in the functional groups of the pendant arms can provide fine tuning of the ligand field for the complexed metal ions. Such approach was successfully employed in our previous study concerning the seven-coordinate Mn II , Fe II , Co II , and Ni II complexes of py 2 -15-pyN 3 O 2 (Figure 1) with two 2-pyridylmethyl pendant arms. [30] Magnetic measurements revealed noticeable values of magnetic anisotropy for [Fe(py 2 -15-pyN 3 O 2 )](ClO 4 ) 2 (D = -7.4 cm -1 ), [Co(py 2 -15-pyN 3 O 2 )](ClO 4 ) 2 (D = 34 cm -1 ), and [Ni(py 2 -15-pyN 3 O 2 )](ClO 4 ) 2 (D = -12.8 cm -1 , E/D = 0.136). Moreover, the slow relaxation of the magnetization was observed [τ 0 = 9.90 × 10 -10 s, U eff = 24.3 K (16.9 cm -1 )] for [Co(py 2 -15-pyN 3 O 2 )](ClO 4 ) 2 . [30] Eur.

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Section: Introductionmentioning

confidence: 99%

Structure and Magnetism of Seven‐Coordinate Fe^III, Fe^II, Co^II and Ni^II Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand

et al. 2018

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“…As a well-known bridging ligand, the cyanide group generally has unique advantages in assembling bimetallic or even trimetallic magnetic CPs, since cyanide-bridged CPs are usually synthesized by a stepwise assembly strategy based on building blocks containing different magnetic carriers (Pardo et al, 2011;Zhang, Xue et al, 2016;Wang, Southerland et al, 2012;Zhang & Sato, 2010;Shatruk et al, 2009). Up to now, in order to clarify the magneto-structural correlation of lowdimensional magnetic systems and to prepare interesting lowdimensional molecule-based magnetic materials, we have developed a series of cyanide building blocks containing larger equatorial plane ligands and two trans-cyanide groups (Zhang et al, 2013;Zhang, Si et al, 2014;Shi, Lan et al, 2018;Shi, Meng et al, 2018;Zhang et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

A cyanide-bridged Fe^III–Mn^II heterobimetallic one-dimensional coordination polymer: synthesis, crystal structure, experimental and theoretical magnetism investigation

Lan

Zhou

et al. 2019

Acta Crystallogr C

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A new cyanide-bridged Fe III -Mn II heterobimetallic coordination polymer (CP), namely catena-poly[[[N,N 0 FeMn(C 18 H 12 N 4 O 2 )(CN) 2 (C 10 H 8 N 2 ) 2 -(CH 3 OH) 2 ]ClO 4 } n , (1), was prepared by the self-assembly of the trans-Á6H 2 O and 4,4 0 -bipyridine, and was structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis shows that CP 1 possesses a cationic linear chain structure consisting of alternating cyanide-bridged Fe-Mn units, with free perchlorate as the charge-balancing anion, which can be further extended into a two-dimensional supramolecular sheet structure via inter-chain interactions between the 4,4 0 -bipyridine ligands. Within the chain, each Mn II ion is six-coordinated by an N 6 unit and is involved in a slightly distorted octahedral coordination geometry. Investigation of the magnetic properties of 1 reveals an antiferromagnetic coupling between the cyanide-bridged Fe III and Mn II ions. A best fit of the magnetic susceptibility based on the one-dimensional alternating chain model leads to the magnetic coupling constants J 1 = À1.35 and J 2 = À1.05 cm À1 , and the antiferromagnetic coupling was further confirmed by spin Hamiltonian-based density functional theoretical (DFT) calculations.

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“…They generate very robust Co II and Mn II complexes with high preference for octahedral coordination and prevent their oxidation to Co III and Mn III , respectively. Moreover, it has been shown that the geometry of these ligands can enhance the local magnetic anisotropy of high [10]. The synthesis of 2 was performed in a glove box operating under argon using degassed solvent by freeze-pump-thaw technique prior to use.…”

Section: Introductionmentioning

confidence: 99%

New bidimensional honeycomb CoII–FeIII and brick wall FeII–CoIII cyanido-bridged coordination polymers: Synthesis, crystal structures and magnetic properties

Dogaru¹,

Ababei²,

Mitcov³

et al. 2014

Polyhedron

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A Cyano-Bridged Cr^IIICo^II Ferromagnet with a Chiral Nanotubular Structure Constituted of Interlocked Single and Double Helices

Cited by 51 publications

References 30 publications

Structure and Magnetism of Seven‐Coordinate Fe^III, Fe^II, Co^II and Ni^II Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand

Structure and Magnetism of Seven‐Coordinate Fe^III, Fe^II, Co^II and Ni^II Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand

A cyanide-bridged Fe^III–Mn^II heterobimetallic one-dimensional coordination polymer: synthesis, crystal structure, experimental and theoretical magnetism investigation

New bidimensional honeycomb CoII–FeIII and brick wall FeII–CoIII cyanido-bridged coordination polymers: Synthesis, crystal structures and magnetic properties

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A Cyano-Bridged CrIIICoII Ferromagnet with a Chiral Nanotubular Structure Constituted of Interlocked Single and Double Helices

Cited by 51 publications

References 30 publications

Structure and Magnetism of Seven‐Coordinate FeIII, FeII, CoII and NiII Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand

Structure and Magnetism of Seven‐Coordinate FeIII, FeII, CoII and NiII Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand

A cyanide-bridged FeIII–MnII heterobimetallic one-dimensional coordination polymer: synthesis, crystal structure, experimental and theoretical magnetism investigation

New bidimensional honeycomb CoII–FeIII and brick wall FeII–CoIII cyanido-bridged coordination polymers: Synthesis, crystal structures and magnetic properties

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A Cyano-Bridged Cr^IIICo^II Ferromagnet with a Chiral Nanotubular Structure Constituted of Interlocked Single and Double Helices

Structure and Magnetism of Seven‐Coordinate Fe^III, Fe^II, Co^II and Ni^II Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand

Structure and Magnetism of Seven‐Coordinate Fe^III, Fe^II, Co^II and Ni^II Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand

A cyanide-bridged Fe^III–Mn^II heterobimetallic one-dimensional coordination polymer: synthesis, crystal structure, experimental and theoretical magnetism investigation