Further Insights into the Role of Temperature in the Synthesis of the Lanthanide(III)‐Pyrazine‐Octacyanotungstate(V) System: an Example of Discrete Materials

Zhou, Hu; Diao, Guowang; Yang, Xiaozhen; Yuan, Aihua; Zhang, Min; Sun, Jing

doi:10.1002/zaac.201300070

Cited by 6 publications

(7 citation statements)

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“…Also, the high connectivity of the octacyanometallate anions combined with the high coordination number of Ln III ions are at the origin of the difficulties to prepare discrete oligonuclear species, their number being very low. 52,61,69,79,80 One efficient approach that provide some control over the molecular structure of Ln IIIcontaining systems is the use of heteroleptic cyanide-bearing metalloligands in the assembling process to afford lowdimensional cyanido-bridged heterospin systems, 81−87 some of them with an interesting SCM behavior 84,87 or layers of SMMs. 85 An alternative route to design cyanido-bridged d−f oligonuclear species or chains is the use of an auxiliary ligand that can block several coordination sites of the lanthanide(III) ions.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The isolation of low-nuclearity/dimensionality 4(5)d–4f complexes is still a challenge because of the unpredictable chemistry of the trivalent rare-earth(III) cations: the strong preference of Ln III ions for hard donor atoms or oxygen-bearing ligands often causes a rapid saturation of the coordination sphere of lanthanide(III) ions with solvent molecules. Also, the high connectivity of the octacyanometallate anions combined with the high coordination number of Ln III ions are at the origin of the difficulties to prepare discrete oligonuclear species, their number being very low. ,,,, One efficient approach that provide some control over the molecular structure of Ln III -containing systems is the use of heteroleptic cyanide-bearing metalloligands in the assembling process to afford low-dimensional cyanido-bridged heterospin systems, − some of them with an interesting SCM behavior , or layers of SMMs . An alternative route to design cyanido-bridged d–f oligonuclear species or chains is the use of an auxiliary ligand that can block several coordination sites of the lanthanide(III) ions. − For example, in the case of cyanido-bridged {Ln III M V } complexes, the tridentate 2,2′:6′,2″-terpyridine (terpy) ligand favored the formation of binuclear and chain structures, , while the bis-bidentate 2,2′-bipyrimidine (bpym) molecule in its reaction with cerium(III) and {W V (CN) 8 } 3– ions afforded tetranuclear complexes, where the polyazine ligand bridges the rare-earth cations .…”

Section: Introductionmentioning

confidence: 99%

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Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

et al. 2017

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A new series of cyanido-bridged {LnW} heterobinuclear complexes of formula [Ln(pyim)(i-PrOH)(HO)(μ-CN)W(CN)]·2HO [Ln = Gd (1), Tb (2), Dy (3), Ho (4), and Er (5); pyim = 2-(1H-imidazol-2-yl)-pyridine) and i-PrOH = isopropyl alcohol] were synthesized by one-pot reaction between (NHBu)[W(CN)] and [Ln(pyim)] complexes (generated in situ by mixing the corresponding Ln ions and the pyim ligand). Compounds 1-5 are isomorphous and crystallize in the monoclinic system P2/n space group. Their crystal structure consists of binuclear units in which the octacyanotungstate(V) anion coordinates to the corresponding Ln ion through a single cyanide ligand. The tungsten(V) and lanthanide(III) ions are eight-coordinated, in distorted square antiprism (W) and distorted trigonal dodecahedron (Ln) geometries, respectively. The direct-current (dc) magnetic properties for 1-5 reveal the occurrence of weak antiferromagnetic interactions between W and Ln cation, with S, F, H, I, and I as ground terms for Gd, Tb, Dy Ho, and Er, respectively [J = -1.19(1) (1), -1.02(2) (2), -1.10(2) (3), -1.30(2) (4), and -1.50(3) cm (5), the spin Hamiltonian being defined as H = -J S·S]. The fit of the χT data of 2-4 points out a positive value for the energy gap between the M components (Δ). This feature is corroborated by their Q-band electron paramagnetic resonance spectra at low temperature, which clearly show M = 0 (2 and 4) and ±1/2 (3 and 5). Incipient frequency-dependent alternating-current magnetic susceptibility signals are observed for 3 and 5 under applied dc fields supporting the presence of slow magnetic relaxation behavior, the blocking temperatures being below 2.0 K. This new series of {LnW} heterobinuclear compounds provides more insights into the exchange magnetic interaction between 5d and 4f centers via the cyanide-bridge, for which scarce information is available to date.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

et al. 2017

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“…And the angles of Dy1–Mo1–Dy1a and Mo1–Dy1–Mo1a are 84.69° and 95.31°, respectively (Table S7), indicating its slight deviation from the square characteristic. This square type tetranuclear structure has been widely reported in cyano-bridged complexes, especially in the charge transfer {Fe 2 Co 2 } system, while it is rare for 4d–4f systems. , The Dy III ions from the opposite corners of the square are capped with two neutral HL ligands in a trans position and two water molecules in a cis position. The eight-coordinated [DyN 2 O 6 ] polyhedron is close to square antiprism configuration with D 4d symmetry (Figure a and Table S8).…”

Section: Resultsmentioning

confidence: 91%

Design of Heterometallic {Ln^III–M^V} (Ln = Dy, Er; M = W, Mo) Molecular Nanomagnets: Protonation Induced Structural Diversification

Mao

Yao

Sun

et al. 2022

Crystal Growth & Design

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The construction of lanthanide-based molecular magnets by a selfassembly strategy of multidentate building blocks and functional ligands is continuing to be a hot research topic. Among them, embedding 4d/5d-based building blocks into 4f molecular nanomagnets is promising as it can bring about more fascinating structures and stronger interactions between 4d/5d and 4f ions. In this work, we report the self-assembly reaction of trivalent lanthanide ions (Dy III , Er III ), multidentate ligand 1,3-di(2-pyridinyl)-1,3-propanedione (HL), and octacyanometallate building blocksErW ); and one bimetallic cation−anionic pair {[Er(HL) 2 (H 2 O) 4 ]•[Mo(CN) 8 ]}•7H 2 O (5 ErMo ) were obtained. Single-crystal X-ray diffraction analyses show that 1 DyW and 2 DyMo crystallize in the monoclinic space group and form neutral cyano-bridged chains; 3 DyMo and 6 ErMo are isostructural complexes that form a rare example of square-type d−f complexes; 4 ErW is a discrete trinuclear complex, and 5 ErMo consists of a {Er(HL) 2 (H 2 O) 4 } 3+ cation and a [Mo(CN) 8 ] 3− anionic moiety. Interestingly, one of the two pyridyl groups in β-diketone ligands is protonated during the formation of 3 DyMo , 5 ErMo , and 6 ErMo , which is uncommon in related complexes. Magnetic analyses reveal that 1 DyW , 2 DyMo , 5 ErMo , and 6 ErMo show field-induced single-molecule magnet (SMM) behaviors, and 3 DyMo is a typical SMM with an energy barrier of 119.6 K under zero dc field. Ab initio calculations were performed on these series of {Ln III −M V } heteronuclear complexes in order to provide more insights into the magnetic exchange interactions between 4d and 4f centers and their influences on the magnetic relaxation properties.

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“…In this regard, the effect of crystallization temperatures on the [ M (CN) 8 ]‐based lanthanide‐metal system have been reported recently by our group . Studies showed that the reaction of lanthanide ions, the bidentate pillar ligand pyrazine and [W(CN) 8 ] 3– units at higher temperatures (38–40 °C) gave rise to 3D pillared frameworks, whereas 2D layers and discrete molecules were generated upon cooling temperatures to T < 33 °C and 0 °C, respectively.…”

Section: Introductionmentioning

confidence: 74%

The Temperature Effect on the Structural Features of Bidentate Ligand‐Decorated Cyanide‐Bridged Mn^II‐Mo^V Compounds

Zhou

et al. 2018

Zeitschrift anorg allge chemie

Self Cite

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The diffusion reaction of Mn2+ ions, the bidentate ligand dabco, and [Mo(CN)8]3– units at different temperatures produced 2D layer [MnII(dabco)MoV(CN)8]2·[MnII(H2O)6]·2H2O (1) and 3D network [MnII(dabco)]2[MnII(CH3OH)4][MoV(CN)8]2·2H2O (2). Structural analysis revealed that there are two independent central Mn atoms (Mn1 and Mn2) in the structure for each compound, which exhibit trigonal bipyramid and octahedral arrangement, respectively. Notably, the coordination mode of the Mn2 unit between layers in both compounds was responsible for the resulting structural dimensionalities. The crystal growth process of final products was dominantly controlled by the kinetics. The isolation of both compounds provides an insight into the effect of crystallization temperatures on the formation and structural conversion of manganese octacyanometalates.

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Further Insights into the Role of Temperature in the Synthesis of the Lanthanide(III)‐Pyrazine‐Octacyanotungstate(V) System: an Example of Discrete Materials

Cited by 6 publications

References 36 publications

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Design of Heterometallic {Ln^III–M^V} (Ln = Dy, Er; M = W, Mo) Molecular Nanomagnets: Protonation Induced Structural Diversification

The Temperature Effect on the Structural Features of Bidentate Ligand‐Decorated Cyanide‐Bridged Mn^II‐Mo^V Compounds

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Further Insights into the Role of Temperature in the Synthesis of the Lanthanide(III)‐Pyrazine‐Octacyanotungstate(V) System: an Example of Discrete Materials

Cited by 6 publications

References 36 publications

Cyanido-Bridged {LnIIIWV} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Cyanido-Bridged {LnIIIWV} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Design of Heterometallic {LnIII–MV} (Ln = Dy, Er; M = W, Mo) Molecular Nanomagnets: Protonation Induced Structural Diversification

The Temperature Effect on the Structural Features of Bidentate Ligand‐Decorated Cyanide‐Bridged MnII‐MoV Compounds

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Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Cyanido-Bridged {Ln^IIIW^V} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

Design of Heterometallic {Ln^III–M^V} (Ln = Dy, Er; M = W, Mo) Molecular Nanomagnets: Protonation Induced Structural Diversification

The Temperature Effect on the Structural Features of Bidentate Ligand‐Decorated Cyanide‐Bridged Mn^II‐Mo^V Compounds