Rational Design of a Ternary Supramolecular System: Self-Assembly of Pentanuclear Lanthanide Helicates

Aroussi, Badr El; Zebret, Soumaila; Besnard, Céline; Perrottet, Philippe; Hamacek, Josef

doi:10.1021/ja204474v

Cited by 96 publications

(46 citation statements)

References 30 publications

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“…The targeted tripodal ligand L1 is synthesized by coupling the activated tris-carboxylic acid 2 with the monoamine compound 3. [19] The targeted octanuclear complex [Eu 8 L1 4 ] 24 + is supposed to be formed by the treatment of L1 with Eu III ,w hich is chosen as ar epresentative cation for the lanthanide series. Moreover, its complexation can be conveniently followed by NMR spectroscopyo rs pectrophotometric methods.…”

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confidence: 99%

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Designing Artificial 3D Helicates: Unprecedented Self‐Assembly of Homo‐octanuclear Tetrapods with Europium

Zebret

Vögele

Klumpler

et al. 2015

Chemistry A European J

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Herein, we report on the rational design, preparation and characterization of a novel homo-octanuclear helicate, which results from a spatial extension of the central tetranuclear platform. The 3D supramolecular assembly is obtained by complexing europium(III) with a new hexatopic tripodal ligand. The isolated octanuclear helicate is fully characterized by different methods clearly evidencing the structure predicted with molecular modelling. The ligand preorganization plays a crucial role in a successful self-assembly process and induces the formation of a well-defined triple-stranded helical structure. This prototypal octanuclear edifice accommodating functional lanthanides within a 3D scaffold offers attractive perspectives for further applications.

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confidence: 99%

“…[19] In L1,t hree strandsa re linked to the same central anchora nd bear two pyridyldicarbonyl coordination moieties connected through as pacer,X ,w hichm ay vary in length or rigidity (Scheme 1). Our choice was finally turned to ad iphenylmethane spacer( dpm = X).…”

mentioning

confidence: 99%

Designing Artificial 3D Helicates: Unprecedented Self‐Assembly of Homo‐octanuclear Tetrapods with Europium

Zebret

Vögele

Klumpler

et al. 2015

Chemistry A European J

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“…With an accurate choice of experimental conditions, the formation of tetra-and penta-nuclear helicates is then possible as reported by Zeckert et al and El Aroussi et al [37,38]. The knowledge of the assembly mechanism and the underlying inter-and intramolecular interactions, allows a fine tuning of targeted properties through the controlled modification of the ligand building block.…”

Section: Lanthanide Helicatesmentioning

confidence: 92%

Heterometallic Complexes Containing Lanthanides

Faulkner

Tropiano

2014

Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials

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The synthesis of tetranuclear gold complexes, as tructurally unprecedented octanuclear complex with ap lanar [Au I 8 ]c ore,a nd pentanuclear [Au I 4 M I ](M = Cu, Ag) complexes is presented. The linear [Au I 4 ]complex undergoes C À Hf unctionalization of carbonyl compounds under mild reaction conditions.I na ddition, [Au I 4 Ag I ]c atalyzes the carbonylation of primary amines to form ureas under homogeneous conditions with efficiencies higher than those achieved by gold nanoparticles. Following the pioneering work of the groups of Hutchings [1] and Haruta [2] on the oxidation of hydrocarbons and CO,many gold clusters and nanoparticles have been structurally characterized and studied in catalysis. [3,4] Recently,s mall gold clusters have been found to activate the CÀIb ond of iodobenzene in the gas phase [5] and to catalyze reactions usually performed by mononuclear gold complexes. [6] However ,t he actual structures of these clusters have not been determined. In this context, it is important to note that the group of Bertrand reported the synthesis of mixed-valence trinuclear [Au 0 2 Au I ]c lusters which are catalysts for the carbonylation of aliphatic amines under homogeneous conditions. [7] As part of our program on the study of the catalytic activity of well-defined gold(I) clusters, [8] we now report ar eady synthesis of linear [Au 4 ], pentagonal [Au I 4 M I ](M= Cu, Ag), and octagonal [Au 8 ]c omplexes.T he linear [Au 4 ] complex reacts with carbonyl compounds by CÀHf unction-alization to form square-planar complexes.F urthermore,t he pentanuclear complex [Au I 4 Ag I ]h as been found to be an excellent homogeneous catalyst for the carbonylation of amines. Our synthesis started from the dinuclear gold(I) complex 1,w hich is quantitatively prepared by mixing 2,6-bis(diphe-Scheme 1. Synthesis of the [Au 4 ]c omplexes 2 and 3 and the [Au 8 ] complex 4.A= SbF 6 ,B= BF 4 .

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“…21). [66] Three equivalents of this large ligand species were able to arrange five lanthanide ions into a tower-like assembly that was capped with one equivalent of the tripodal ligand L26 (Fig 21). This system represented an excellent example of rational ligand design being used to isolate large assemblies in a predictable manner.…”

Section: Higher-order Assembliesmentioning

confidence: 99%

Lanthanide-based self-assemblies of 2,6-pyridyldicarboxamide ligands: Recent advances and applications as next-generation luminescent and magnetic materials

Kitchen

2017

Coordination Chemistry Reviews

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Please cite this article as: J.A. Kitchen, Lanthanide-based self-assemblies of 2,6-pyridyldicarboxamide ligands: recent advances and applications as next-generation luminescent and magnetic materials, Coordination Chemistry Reviews (2017), doi: http://dx.doi.org/10. 1016/j.ccr.2017.01.012 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Rational Design of a Ternary Supramolecular System: Self-Assembly of Pentanuclear Lanthanide Helicates

Cited by 96 publications

References 30 publications

Designing Artificial 3D Helicates: Unprecedented Self‐Assembly of Homo‐octanuclear Tetrapods with Europium

Designing Artificial 3D Helicates: Unprecedented Self‐Assembly of Homo‐octanuclear Tetrapods with Europium

Heterometallic Complexes Containing Lanthanides

Lanthanide-based self-assemblies of 2,6-pyridyldicarboxamide ligands: Recent advances and applications as next-generation luminescent and magnetic materials

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