A Rare‐Earth Metal TCNQ Magnet: Synthesis, Structure, and Magnetic Properties of {[Gd2(TCNQ)5(H2O)9][Gd(TCNQ)4(H2O)3]}⋅4 H2O

Zhao, Huaiqing; Bazile, Mervin J.; Galán‐Mascarós, José Ramón; Dunbar, Kim R.

doi:10.1002/anie.200390259

Cited by 100 publications

(25 citation statements)

References 41 publications

(2 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1D) have been previously employed for the engineering of 2D metal-organic networks on surfaces with transition metal centers, where threefold and fourfold coordination nodes prevail (30, 32). Carbonitrile endgroups have also been successfully used for synthesis of 3D lanthanide-organic compounds, mainly targeting molecular magnetic materials (33)(34)(35). Here, as with other systems, the lanthanide ions typically present high coordination numbers, ranging from 6 to 12 (31).…”

Section: Resultsmentioning

confidence: 99%

Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly

Écija

Urgel

Papageorgiou

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

127

109

View full text Add to dashboard Cite

The tessellation of the Euclidean plane by regular polygons has been contemplated since ancient times and presents intriguing aspects embracing mathematics, art, and crystallography. Significant efforts were devoted to engineer specific 2D interfacial tessellations at the molecular level, but periodic patterns with distinct five-vertex motifs remained elusive. Here, we report a direct scanning tunneling microscopy investigation on the ceriumdirected assembly of linear polyphenyl molecular linkers with terminal carbonitrile groups on a smooth Ag(111) noble-metal surface. We demonstrate the spontaneous formation of fivefold Celigand coordination motifs, which are planar and flexible, such that vertices connecting simultaneously trigonal and square polygons can be expressed. By tuning the concentration and the stoichiometric ratio of rare-earth metal centers to ligands, a hierarchic assembly with dodecameric units and a surface-confined metalorganic coordination network yielding the semiregular Archimedean snub square tiling could be fabricated.T he tiling of surfaces is relevant for pure art (1), mathematics (2, 3), material physics (4), and molecular science (5). Johannes Kepler's pertaining, rigorous analysis revealed four centuries ago that in the Euclidean plane 11 tessellations based on symmetric polygonal units exist (6): three consist of a specific polygon (so-called regular tilings with squares, triangles, or hexagons, respectively), whereas eight require the combination of two or more different polygons (named semiregular or Archimedean tilings from triangles, squares, hexagons, octagons, and dodecagons).Manifestations of regular tessellations at the atomic and molecular level are ubiquitous, including crystalline planes and surfaces of elemental or molecular crystals, and honeycomb structures encountered, e.g., for graphene sheets, strain relief and supramolecular lattices. In addition, the family of semiregular Archimedean tilings features intriguing characteristics. They may represent geometrically frustrated magnets (7) or provide novel routes for constructing photonic crystals (8). However, with the exception of the frequently realized trihexagonal tiling (also known as the Kagomé lattice) (9-15), the other semiregular Archimedean tiling patterns remain largely unexplored.Three of the semiregular Archimedean tilings correspond to five-vertex configurations (Fig. 1 A-C): the snub hexagonal tiling (four triangles and one hexagon at each vertex, labeled 3.3.3.3.6), the elongated triangular tiling (three triangles and two squares join at each vertex in a 3.3.3.4.4 sequence), and the snub square tiling (three triangles and two squares at each vertex; labeled 3.3.4.3.4). They have been identified in bulk materials, such as layered crystalline structures of complex metallic alloys (4, 16-18), supramolecular dendritic liquids (19), liquid crystals (20), special star-branched polymers (21, 22), and binary nanoparticle superlattices (23). Moreover, recent experiments with colloids at a quasicrystalline substra...

show abstract

Section: Resultsmentioning

confidence: 99%

Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly

Écija

Urgel

Papageorgiou

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

127

109

View full text Add to dashboard Cite

show abstract

“…[104] , which consist of alternating anionic and cationic layers perpendicular to the c axis, exhibiting different ratios of Gd(Ⅲ) and TCNQ -· radicals, both of which are based on a 2D network of Gd(Ⅲ) ions coordinated by TCNQ radical anions (Figure 14 left). The different ratios of Gd(Ⅲ) and TCNQ −· in the two independent layers lead to the unusual existence of both cationic and anionic networks.…”

Section: Magnetic Ordering Of 4f-p Molecular Materialsmentioning

confidence: 99%

“…Tetracyanoethylene (TCNE) and tetracyanodimethane (TCNQ) radicals are also effective spin carriers to couple with Gd(Ⅲ) ions. It is worth mentioning that TCNQ can link the Gd(Ⅲ) to form extended structure and behave as a ferrimagnet at low temperatures [103,104] .…”

Section: Magnetic Coupling In 4f-p Systemsmentioning

confidence: 99%

Magnetic molecular materials with paramagnetic lanthanide ions

Wang

Jiang

Wang

et al. 2009

Sci. China Ser. B-Chem.

View full text Add to dashboard Cite

The diverse magnetic properties of lanthanide-based magnetic molecular materials are introduced in the following organization. First, the general aspects of magnetic molecular materials and electronic states of lanthanide ions are introduced. Then the structures and magnetic properties are described and analyzed for molecules with one lanthanide ion, 4f-4f, 4f-3d and 4f-p magnetic coupling interactions. In each section, magnetic coupling, magnetic ordering and magnetic relaxation phenomenon are briefly reviewed using some examples. Finally, some possibilities of developing magnetic molecular materials containing lanthanide ions are discussed in the outlook part.

show abstract

“…

The self-assembly of organic TCNQFC À radicals (2fluoro-7,7,8,8-tetracyano-p-quinodimethane) and the anisotropic [Tb(valpn)Cu] 3+ dinuclear cations produced a singlechain magnet (SCM) involving stacking interactions of TCNQFC À radicals (H 2 valpn is the Schiff base from the condensation of o-vanillin with 1,3-diaminopropane). [2] These characteristics of TCNQ radicals render them excellent candidates for the elaboration of magnetic and conducting bifunctional materials. [1] In particular, TCNQ radicals readily form columnar stacks which allows for excellent electron transport for the resulting materials.

…”

mentioning

confidence: 99%

Single‐Chain Magnetic Behavior in a Hetero‐Tri‐Spin Complex Mediated by Supramolecular Interactions with TCNQF^.− Radicals

Wang

Zhang

et al. 2014

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

The self-assembly of organic TCNQF˙⁻ radicals (2-fluoro-7,7,8,8-tetracyano-p-quinodimethane) and the anisotropic [Tb(valpn)Cu](3+) dinuclear cations produced a single-chain magnet (SCM) involving stacking interactions of TCNQF˙⁻ radicals (H2valpn is the Schiff base from the condensation of o-vanillin with 1,3-diaminopropane). Static and dynamic magnetic characterizations reveal that the effective energy barrier for the reversal of the magnetization in this hetero-tri-spin SCM is significantly larger than the barrier of the isolated single-molecule magnet based on the {TbCu} dinuclear core.

show abstract

A Rare‐Earth Metal TCNQ Magnet: Synthesis, Structure, and Magnetic Properties of {[Gd₂(TCNQ)₅(H₂O)₉][Gd(TCNQ)₄(H₂O)₃]}⋅4 H₂O

Cited by 100 publications

References 41 publications

Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly

Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly

Magnetic molecular materials with paramagnetic lanthanide ions

Single‐Chain Magnetic Behavior in a Hetero‐Tri‐Spin Complex Mediated by Supramolecular Interactions with TCNQF^.− Radicals

Contact Info

Product

Resources

About

A Rare‐Earth Metal TCNQ Magnet: Synthesis, Structure, and Magnetic Properties of {[Gd2(TCNQ)5(H2O)9][Gd(TCNQ)4(H2O)3]}⋅4 H2O

Cited by 100 publications

References 41 publications

Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly

Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly

Magnetic molecular materials with paramagnetic lanthanide ions

Single‐Chain Magnetic Behavior in a Hetero‐Tri‐Spin Complex Mediated by Supramolecular Interactions with TCNQF.− Radicals

Contact Info

Product

Resources

About

A Rare‐Earth Metal TCNQ Magnet: Synthesis, Structure, and Magnetic Properties of {[Gd₂(TCNQ)₅(H₂O)₉][Gd(TCNQ)₄(H₂O)₃]}⋅4 H₂O

Single‐Chain Magnetic Behavior in a Hetero‐Tri‐Spin Complex Mediated by Supramolecular Interactions with TCNQF^.− Radicals