Magnetic Ordering in Self‐assembled Materials Consisting of Cerium(III) Ions and the Radical Forms of 2,5‐TCNQX<sub>2</sub> (X=Cl, Br)

Ballesteros-Rivas, María F.; Zhao, Huaiqing; Prosvirin, Andrey V.; Reinheimer, Eric W.; Toscano, Rubén A.; Valdés-Martı́nez, Jesús; Dunbar, Kim R.

doi:10.1002/ange.201107938

Cited by 3 publications

(3 citation statements)

References 54 publications

(24 reference statements)

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“…22,23 Carbonitrile species were also used to synthesize lanthanide−organic compounds in solution targeting luminescent metal−organic frameworks 24 or molecular magnetic materials. 25,26 Inspired by these promising results, we realized Ln-directed architectures on coinage metals. 27−31 The prevailing expression of mononuclear nodes with large coordination numbers and planar geometry notably entails complex network organizations.…”

Section: ■ Nitrogen-donor Ligandsmentioning

confidence: 99%

Lanthanide-Directed Assembly of Interfacial Coordination Architectures–From Complex Networks to Functional Nanosystems

et al. 2018

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Metallo-supramolecular engineering on surfaces provides a powerful strategy toward low-dimensional coordination architectures with prospects for several application fields. To date, most efforts have relied on transition metal centers, and only recently did we pioneer lanthanide-directed assembly. Coordination spheres and motifs with rare-earth elements generally display distinct properties and structural features. The size of the cations and shielding role of the 4f orbitals induces high coordination numbers, frequently entailing flexible coordination geometries. Following Pearson's hard and soft acid-base theory, lanthanide cations are hard Lewis acids and thus feature strong affinity for nitrile, terpyridine, and carboxylate donor moieties. The prevailing oxidation state is +3, although in certain compounds stable +2 or +4 cations occur. The chemistry of rare-earth elements is currently receiving widespread attention, as they are key ingredients for established and emerging 21st century science and technology with relevance for energy conversion, sensing, catalysis, magnetism, photonics, telecommunications, superconductivity, biomedicine, and quantum engineering. In this Account, we review recent advances toward the design of interfacial supramolecular nanoarchitectures incorporating lanthanide centers. We apply controlled ultrahigh vacuum conditions whereby atomistically clean substrates are prepared and exposed to ultrapure atomic and molecular beams of the chosen sublimable constituents. We focus on direct molecular-level investigations and in situ assembly operative close to equilibrium conditions. Our scanning probe microscopy techniques provide atomistic insights regarding the formation, stability, and manipulability of metal-organic compounds and networks. In order to gain deeper insights into the experimental findings, complementary computational analysis of bond characteristics, electronic properties, and coordination motifs has been performed for several case studies. Exemplary elements under consideration include cerium, gadolinium, dysprosium, and europium. By the use of ditopic molecular linkers equipped with carbonitrile moieties, adaptive coordination spheres are unveiled, yielding vertices with two- to sixfold symmetry. The respective coordination nodes underlie the expression of complex networks, such as semiregular Archimedean tessellations for cerium- or gadolinium-directed assemblies and random-tiling quasicrystalline characteristics for europium. Tunability via constituent stoichiometry regulation is revealed for bimolecular arrangements embedding europium centers, simultaneously connecting to carbonitrile and terypyridine ligands. Ditopic carboxylate linkers yield robust reticular networks based on a lateral coordination number of 8 for either gadolinium or dysprosium complexation, featuring a prevalent ionic nature of the coordination bond. Orthogonal insertion protocols give rise to d-f reticular architectures exploiting macrocyclic tetradentate cobalt complexation and peripheral carbon...

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Section: ■ Nitrogen-donor Ligandsmentioning

confidence: 99%

Lanthanide-Directed Assembly of Interfacial Coordination Architectures–From Complex Networks to Functional Nanosystems

et al. 2018

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“…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).…”

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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

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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...

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“…Owing to theirsuperiorproperties in luminescence [1], magnetism [2], catalysis [3], and so forth,the rare earth complexes have been of interest for many years.In early studies, the synthesis of these complexes is mainly carried out in organic solvents. However, organic solvents are toxic, expensive, and environmentally harmful, greatly hindering the development of rare earth complexes.…”

Section: Introductionmentioning

confidence: 99%

Aqueous Synthesis and Thermal Decomposition Behavior of Rare Earth Complexes with <i>o</i>-Carboxylbenzaldehyde-2-Pyrroleformylhydrazone Ligand

Yang

Liu

Wang

et al. 2013

AMR

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Thirteen novel complexeswere synthesized using this method, by employing the designed ligand o-carboxylbenzaldehyde-2-pyrroleformylhydrazone (H2L). Elemental analysis, molar conductivity,Fourier transform infrared (FTIR) spectracharacterizations show that the composition formula of the complexes is RE(HL)(H2L)•2H2O (where RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Y). The thermal decomposition of the thirteen complexes was studied by Subscript textTG-DTG analysis and their apparent activation energies (E) were calculated by Kissinger’s and Flynn-Wall-Ozawa’s methods.

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Magnetic Ordering in Self‐assembled Materials Consisting of Cerium(III) Ions and the Radical Forms of 2,5‐TCNQX₂ (X=Cl, Br)

Cited by 3 publications

References 54 publications

Lanthanide-Directed Assembly of Interfacial Coordination Architectures–From Complex Networks to Functional Nanosystems

Lanthanide-Directed Assembly of Interfacial Coordination Architectures–From Complex Networks to Functional Nanosystems

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

Aqueous Synthesis and Thermal Decomposition Behavior of Rare Earth Complexes with <i>o</i>-Carboxylbenzaldehyde-2-Pyrroleformylhydrazone Ligand

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Magnetic Ordering in Self‐assembled Materials Consisting of Cerium(III) Ions and the Radical Forms of 2,5‐TCNQX2 (X=Cl, Br)

Cited by 3 publications

References 54 publications

Lanthanide-Directed Assembly of Interfacial Coordination Architectures–From Complex Networks to Functional Nanosystems

Lanthanide-Directed Assembly of Interfacial Coordination Architectures–From Complex Networks to Functional Nanosystems

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

Aqueous Synthesis and Thermal Decomposition Behavior of Rare Earth Complexes with <i>o</i>-Carboxylbenzaldehyde-2-Pyrroleformylhydrazone Ligand

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Magnetic Ordering in Self‐assembled Materials Consisting of Cerium(III) Ions and the Radical Forms of 2,5‐TCNQX₂ (X=Cl, Br)