A Heterotetranuclear [NiIIReIV3] Single-Molecule Magnet

Martı́nez-Lillo, José; Armentano, Donatella; Munno, Giovanni De; Wernsdorfer, Wolfgang; Julve, Miguel; Lloret, Francesc; Faus, Juan

doi:10.1021/ja0643873

Cited by 94 publications

(83 citation statements)

References 19 publications

(14 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…4,5 The magnetic properties of the mononuclear hexahalorhenate(IV) anions, of general formula [ReX6] 2-(X = F, Cl, Br, I), have been thoroughly investigated for decades. 6 In general, hexahalorhenate(IV) salts of diamagnetic, univalent cations show significant antiferromagnetic interactions, which are transmitted in the crystal lattice of these systems through Re-X···X-Re intermolecular contacts, between the paramagnetic and highly anisotropic Re IV centres (5d 3 ion with t2g 3 configuration). 6 Given that the intermolecular halogen···halogen distance depends on the countercation size, bulky organic cations such as tetraphenylarsonium (AsPh4) + and tetra-n-butylammonium (NBu4) + preclude the magnetic coupling between adjacent hexahalorhenate(IV) anions.…”

Section: The Effect Of Protonated Organic Cations and Anion-π Interacmentioning

confidence: 99%

“…6 In general, hexahalorhenate(IV) salts of diamagnetic, univalent cations show significant antiferromagnetic interactions, which are transmitted in the crystal lattice of these systems through Re-X···X-Re intermolecular contacts, between the paramagnetic and highly anisotropic Re IV centres (5d 3 ion with t2g 3 configuration). 6 Given that the intermolecular halogen···halogen distance depends on the countercation size, bulky organic cations such as tetraphenylarsonium (AsPh4) + and tetra-n-butylammonium (NBu4) + preclude the magnetic coupling between adjacent hexahalorhenate(IV) anions. 6 However, paramagnetic cations can also provide new insights into the magnetic properties of this family of materials, indeed studies of hexachlororhenate(IV) salts of organic radicals, 7a organometallic ferrocenium 7b and ruthenium(III) 7c cations revealed the occurrence of other magnetic phenomena, such as ferromagnetism and spin canting.…”

Section: The Effect Of Protonated Organic Cations and Anion-π Interacmentioning

confidence: 99%

“…6 Given that the intermolecular halogen···halogen distance depends on the countercation size, bulky organic cations such as tetraphenylarsonium (AsPh4) + and tetra-n-butylammonium (NBu4) + preclude the magnetic coupling between adjacent hexahalorhenate(IV) anions. 6 However, paramagnetic cations can also provide new insights into the magnetic properties of this family of materials, indeed studies of hexachlororhenate(IV) salts of organic radicals, 7a organometallic ferrocenium 7b and ruthenium(III) 7c cations revealed the occurrence of other magnetic phenomena, such as ferromagnetism and spin canting. 6,7c The most investigated [ReX6] 2− salts to date are those obtained with the hexachlororhenate(IV) anion.…”

Section: The Effect Of Protonated Organic Cations and Anion-π Interacmentioning

confidence: 99%

“…At room temperature the MT values are 1.58 (1) and 1.59 cm 3 mol -1 K (2), which are as expected for a magnetically isolated Re IV (5d 3 , S = 3/2 with t2g 3 configuration) mononuclear complex with g = 1.8-1.9. [6][7][8]10 Upon cooling, MT for 1 remains practically constant until 50 K, then decreases at lower temperatures reaching a minimum value of 0.88 cm 3 mol -1 K at 2.0 K. No maximum of the susceptibility is observed in 1 (inset in Fig. S5).…”

Section: The Effect Of Protonated Organic Cations and Anion-π Interacmentioning

confidence: 99%

See 3 more Smart Citations

Effect of Protonated Organic Cations and Anion−π Interactions on the Magnetic Behavior of Hexabromorhenate(IV) Salts

Martı́nez-Lillo

Pedersen

Faus

et al. 2015

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

Two novel Re IV compounds of formula (Hbpym) 2 [Re IV Br 6 ]•4H 2 O (1) and (H 4 biim)[Re IV Br 6 ]•4H 2 O (2) [Hbpym + = 2,2′-bipyrimidinium cation and H 4 biim 2+ = 2,2′-biimidazolium dication] have been prepared and magnetostructurally characterized. 1 and 2 exhibit distinct crystal packing, and the presence of weak intermolecular contacts, such as Re−Br•••Br−Re (1 and 2), Re− Br•••(H 2 O)•••Br−Re (1 and 2), and Re−Br•••π•••Br−Re ( 2), lead to different magnetic behaviors. While 1 is antiferromagnetic, 2 is a ferromagnetic compound and indeed the first example of ferromagnetic salt based on the hexabromorhenate(IV) anion. These results suggest a straightforward synthetic route to the preparation of new ferromagnetically coupled Re IV compounds.

show abstract

Section: The Effect Of Protonated Organic Cations and Anion-π Interacmentioning

confidence: 99%

Section: The Effect Of Protonated Organic Cations and Anion-π Interacmentioning

confidence: 99%

Section: The Effect Of Protonated Organic Cations and Anion-π Interacmentioning

confidence: 99%

Section: The Effect Of Protonated Organic Cations and Anion-π Interacmentioning

confidence: 99%

See 2 more Smart Citations

Effect of Protonated Organic Cations and Anion−π Interactions on the Magnetic Behavior of Hexabromorhenate(IV) Salts

Martı́nez-Lillo

Pedersen

Faus

et al. 2015

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

show abstract

“…[23,24] In contrast to inorganic medicinal chemistry, paramagnetic rhenium complexes have received some attention in the design of single-molecule magnets (SMM). [19,[25][26][27][28] Here a brief diversion is here needed for a broader perspective. About 20 years ago, the molecular cluster [Mn 12 O 12 (CH 3 CO 2 ) 16 (H 2 O) 4 ] was discovered to exhibit slow magnetic relaxation at low temperatures.…”

Section: Introductionmentioning

confidence: 99%

A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

Zobi

2010

Chimia

View full text Add to dashboard Cite

Transition metal complexes of rhenium and technetium find wide application in nuclear medicine and the chemistry of these elements is still the focus of intense research efforts. For therapeutic and diagnostic applications, currently much attention is dedicated to the development of new targeting strategies aimed at appending the metal complexes to biological vectors (e.g. a peptide) for a site-specific delivery of the radio-nuclides. Advancements in radiopharmacy, however, will not only arise from the development of new targeted strategies but also from the exploration of the chemistry of these elements in their unusual oxidation states. In this respect the even number oxidation states of Re and Tc (i.e. +II, +IV and +VI) are relatively poorly understood. In particular, stable and substitutionally labile mononuclear 17-electron species of the elements (+II, d (5)) are a rarely encountered class of complexes. In this review we present our recent developments in the field of rhenium (II) chemistry with emphasis on the novel synthetic strategies we have recently introduced. We will also describe how the unique chemical and electronic properties of Re(II)-based complexes may provide a potentially new approach for applications in inorganic medicinal chemistry.

show abstract

A Docosanuclear {Mo₈Mn₁₄} Cluster Based on [Mo(CN)₇]⁴⁻

2010

View full text Add to dashboard Cite

One of the recent strategies being explored for obtaining molecular magnets with enhanced properties is the incorporation of heavier transition metals from the 4d and 5d metal ions. [1][2][3] A central player in this area of research is the cyanide ligand, which can be used to prepare mixed metal clusters with unusual properties. [4] Of particular interest is the fact that cyanide molecules containing 4d or 5d ions or combinations of them with 3d ions have been predicted to behave as singlemolecule magnets (SMMs) with higher blocking temperatures T B than those based on 3d ions. They are also expected to exhibit properties such as anisotropic magnetic exchange interactions. [5] A main driving force for the high activity in cyanide magnetism is that the use of cyanometalates in reactions with metal ions equipped with capping ligands present several advantages, such as control over the sign of magnetic interactions in most cases and also predictable structures based on the building block approach. Magnetic anisotropy can be conveniently introduced by choosing the appropriate preformed 4d or 5d cyanometalate anion. The observation of SMM behavior with 4d and 5d metal ions with oxygen-type bridging ligands is limited to only one case, [6] but there are a number of SMMs from the heavier congeners of Groups 6 and 7 with the precursors [(Me 3 tacn)Mo III (CN) 3 ], [7] [Mo V (CN) 8 ] 3À , [8,9] [W V (CN) 8 ] 3À , [8][9][10] [Re IV (CN) 7 ] 3À , [11] and [(triphos)Re II (CN) 3 ] À . [12] In contrast to the widely investigated anion [Mo V (CN) 8 ] 3À , [2,8,9] the heptacyanomolybdate derivative [Mo III (CN) 7 ] 4À has received much less attention in the molecular magnetism field, presumably because of the synthetic challenges in the preparation and handling of this anion. Unlike the hexa-and octacyanometalates, the [Mo III (CN) 7 ] 4À anion favors low-symmetry extended structures with pronounced magnetic anisotropy. [1,13] The results of theoretical investigations have suggested that [Mo(CN) 7 ] 4À will be useful for the design of SMMs with high T B values as a result of its strong anisotropic exchange properties. [5] Despite such promising predictions, magnetic materials based on [Mo(CN) 7 ] 4À are relatively scarce, with the exception of the pioneering work of Kahn and co-workers, and subsequent studies by several other research groups, who prepared a number of two-and three-dimensional magnets with the [Mo(CN) 7 ] 4À and Mn II ions. [1,13] The only other reports are an amorphous compound with iron(II) [14] and two microcrystalline materials with vanadium(II) and nickel(II). [15] To our knowledge, no discrete clusters based on [Mo(CN) 7 ] 4À have been reported.Given the aforementioned considerations, we recently devoted efforts to the preparation of mixed-metal molecules that contain the [Mo(CN) 7 ] 4À building block. Herein, we report the first discrete compound based on [Mo(CN) 7 ] 4À

show abstract

A Heterotetranuclear [Ni^IIRe^IV₃] Single-Molecule Magnet

Cited by 94 publications

References 19 publications

Effect of Protonated Organic Cations and Anion−π Interactions on the Magnetic Behavior of Hexabromorhenate(IV) Salts

Effect of Protonated Organic Cations and Anion−π Interactions on the Magnetic Behavior of Hexabromorhenate(IV) Salts

A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

A Docosanuclear {Mo₈Mn₁₄} Cluster Based on [Mo(CN)₇]⁴⁻

Contact Info

Product

Resources

About

A Heterotetranuclear [NiIIReIV3] Single-Molecule Magnet

Cited by 94 publications

References 19 publications

Effect of Protonated Organic Cations and Anion−π Interactions on the Magnetic Behavior of Hexabromorhenate(IV) Salts

Effect of Protonated Organic Cations and Anion−π Interactions on the Magnetic Behavior of Hexabromorhenate(IV) Salts

A Different 'Spin' on Rhenium Chemistry. Synthetic Approaches and Perspectives of 17-Electron Rhenium Complexes

A Docosanuclear {Mo8Mn14} Cluster Based on [Mo(CN)7]4−

Contact Info

Product

Resources

About

A Heterotetranuclear [Ni^IIRe^IV₃] Single-Molecule Magnet

A Docosanuclear {Mo₈Mn₁₄} Cluster Based on [Mo(CN)₇]⁴⁻