Mapping the Sequential Self‐Assembly of Heterometallic Clusters: From a Helix to a Grid

Over the last two decades the field of metallosupramolecular self-assembly has emerged as a promising research area for the development of intricate, three-dimensional structures of increasing complexity and functionality. The advent of this area of research has strongly benefited from design principles that considered the ligand geometry and metal coordination geometry, thus opening up routes towards rationally designed classical (Archimedean or Platonic) architectures. In this tutorial review, we will focus on more recent developments in the design and synthesis of three-dimensional suprastructures which have non-classical architectures (non-Archimedean/Platonic solids) and we will explicitly address the secondary effects responsible for their formation. Three classes of metallosupramolecular assemblies will be discussed: architectures formed through the combination of a single ligand and metal, heteroleptic structures and heterometallic structures. It is hoped that our exposition may suggest how different principles employed in these three classes of structures might be combined to create even greater complexity and potential for function.

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“…84 This ligand has been shown to form a mixed Co II /Co III grid. 85 The group have developed structures incorporating both cobalt and iron.…”

Section: Heterometallic Structuresmentioning

confidence: 99%

Building on architectural principles for three-dimensional metallosupramolecular construction

et al. 2013

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“…The 2,6‐bis(1H‐pyrazol‐3‐yl)pyridine and derivatives have recently used for synthesis of polynuclear complexes . Significantly, Oshio and Cronin and coworkers reported the sequential self‐assembly of heterometallic clusters from a helix to a grid using the ligand 2,6‐bis[5‐2‐pyridinyl]‐1H‐pyrazol‐3‐yl]pyridine as shown in Figure .…”

Section: Supramolecular Architectures With Di‐pyrazolesmentioning

confidence: 99%

“…Significantly, Oshio and Cronin and coworkers reported the sequential self‐assembly of heterometallic clusters from a helix to a grid using the ligand 2,6‐bis[5‐2‐pyridinyl]‐1H‐pyrazol‐3‐yl]pyridine as shown in Figure . A heptanuclear [Fe(III) 2 Co(II) 5 (H 2 L) 6 O 6 (H 2 O) 6 ] (BF 4 ) 4 helical complex and a [3×3] grid [Fe(II) 4 Fe(III)Co(II) 4 (H 2 L) 6 (OH) 12 (H 2 O) 6 ] (BF 4 ) 7 were obtained by the subtle one‐pot reactions with different Fe/Co ratios with the ligand under ambient conditions . Time‐resolved ESI‐MS experiments to monitor the self‐assembly processes suggested the pathway of the transformation from helix to grid.…”

Section: Supramolecular Architectures With Di‐pyrazolesmentioning

confidence: 99%

From Metal‐Metal Bonding to Supra‐Metal‐Metal Bonding Directed Self‐Assembly: Supramolecular Architectures of Group 10 and 11 Metals with Ligands from Mono‐ to Poly‐Pyrazoles

2018

Israel Journal of Chemistry

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The supramolecular architectures of pyrazole ligands with polynuclear metal centers have established a wide variety of constructing motifs. This review focuses on the metal‐metal bonding and Supra‐Metal‐Metal Bonding directed self‐assembly of supramolecular architectures of pyrazole ligands ranging from simple mono‐pyrazoles and derivatives to bipyrazoles and polypyrazoles with group 10 and 11 elements. The utility of the constructing motifs (μ‐pyrazolato‐N,N′)2 doubly‐bridged dimetal corners in the metal‐metal‐bonding directed self‐assembly approaches with spontaneous deprotonation from bipyrazole to tripyrazole and tetrapyrazolyl calix[4]arene ligands, metallomacrocyclic and cage‐like complexes have been synthesized. The proton switching programmable self‐assembly strategy using pyrazole‐based bifunctional ligands has been developed by Yu. They have obtained organic homo‐ or hetero‐metallic supramolecular complexes from macrocycles, cages, to one dimensional polymers.

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“…The choice of ligand lies in two main factors, namely, rigidity (to minimize variability) and the use of polytopic coordination sites (to ensure multiple metal centers are coordinated) (e.g. pyridazine, pyrimidine, phenoxide) [7][8][9][10][11][12][13][14]. N 3 -(2-pyridoyl)-2-pyridinecarboxamidrazone and analogs are often employed to construct homometallic or heterometallic [2þ2] molecular grids [1][2][3].…”

Section: Introductionmentioning

confidence: 99%

2-(1H-pyrazol-3-yl)pyrazine: a polytopic N-donor ligand used to construct Cu-[2+2] molecular grid: synthesis, structure, and magnetic properties

Feng¹,

Yang²,

Liao³

et al. 2011

Journal of Coordination Chemistry

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Herein, we present a new polytopic N-donor, which is used to construct a metal-organic compound. The resulting metal-organic compound, Cu 4 (L) 6 (NO 3 ) 2 (HL¼(1H-pyrazol-3-yl)pyrazine) (1), is synthesized by the hydrothermal reaction of Cu(NO 3 ) 2 and HL (ratio: 1 : 1). Single-crystal X-ray diffraction shows that 1 comprises a Cu-[2þ2] molecular grid. Magnetic studies reveal antiferromagnetic interactions, interpreted by a simplified dinuclear mode.

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Mapping the Sequential Self‐Assembly of Heterometallic Clusters: From a Helix to a Grid

Cited by 64 publications

References 29 publications

Building on architectural principles for three-dimensional metallosupramolecular construction

Building on architectural principles for three-dimensional metallosupramolecular construction

From Metal‐Metal Bonding to Supra‐Metal‐Metal Bonding Directed Self‐Assembly: Supramolecular Architectures of Group 10 and 11 Metals with Ligands from Mono‐ to Poly‐Pyrazoles

2-(1H-pyrazol-3-yl)pyrazine: a polytopic N-donor ligand used to construct Cu-[2+2] molecular grid: synthesis, structure, and magnetic properties

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