Anion‐Templated Assembly of Half‐Sandwich Rhodium‐Based Multinuclear Metallamacrocycles

Wang, Guoliang; Lin, Yue‐Jian; Jin, Guo‐Xin

doi:10.1002/chem.201003167

Cited by 24 publications

(22 citation statements)

References 101 publications

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“…150 The size of the counteranion significantly affects the nuclearity of the final self-assembled macrocycles. While larger counteranions OTf − , PF 6 − and SbF 6 − favor the formation of hexanuclear metallamacrocycles, BF 4 − favors the formation of a tetranuclear metallamacrocycle.…”

Section: Two-dimensional (2d) Ensemblesmentioning

confidence: 99%

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

2011

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Section: Two-dimensional (2d) Ensemblesmentioning

confidence: 99%

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

2011

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“…These differences depend on several factors: the nature of the metal centers, the shape of the linker ligand, the donor types and so on. [30] In specific templated assemblies of metallamacrocycles, the coordination model of the metal is the main factor that determines the nuclearity and geometry of the macrocycle formed. Because of this, the amount of sodium acetate and the solvent used for crystallization was found to promote the formation of complex 5.…”

Section: Discussionmentioning

confidence: 99%

Half-sandwich rhodium and iridium fragments and carboxylate ligands as building blocks for the formation of metallamacrocycles

Lin

Fan

Jin

2017

Journal of Organometallic Chemistry

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A series of half-sandwich rhodium and iridium complexes containing carboxylate ligands were synthesized and characterized. Reactions between [Cp*MCl 2 ] 2 (M = Ir or Rh) and 1,3,6bis(2-pyridyl)-1,2,4,5-tetrazine (L1) gave binuclear complexes 1 and 2 under different conditions. The half-sandwich iridium and rhodium metallamacrocycles complexes 3-5 were constructed in a stepwise manner by the addition of carboxylate ligands (sodium acetate or the conjugate bases of pyrazine-2,3-dicarboxylic acid or 3-(2-pyridyl)acrylic acid) to the solution of the binuclear precursors prepared from the reactions of [Cp*MCl 2 ] 2 (M = Rh or Ir) with linear N,N′-donor ligands (4,4′bipyridine or trans-1,2-bis(4-pyridyl)ethylene), respectively. The structures of binuclear complexes and tetranuclear macrocycles were confirmed by elemental analysis, IR, 1 H NMR spectroscopy and single-crystal X-ray diffraction.

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“…34 The anion-templated assembly of a series of rhodium-based multinuclear metallacycles was investigated in detail. 35 …”

Section: ■ Other Metallacyclesmentioning

confidence: 97%

Half-Sandwich Iridium- and Rhodium-based Organometallic Architectures: Rational Design, Synthesis, Characterization, and Applications

2014

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CONSPECTUS: Over the last two decades, researchers have focused on the design and synthesis of supramolecular coordination complexes, which contain discrete functional structures with particular shapes and sizes, and are similar to classic metal-organic frameworks. Chemists can regulate many of these systems by judiciously choosing the metal centers and their adjoining ligands. These resulting complexes have unusual properties and therefore many applications, including molecular recognition, supramolecular catalysis, and some applications as nanomaterials. In addition, researchers have extensively developed synthetic methodologies for the construction of discrete self-assemblies. One of the most important challenges for scientists in this area is to be able to synthesize target structures that can be controlled in both length and width. For this reason, it is important that we understand the factors leading to special shapes and sizes of such architectures, especially how starting building blocks and functional ligands affect the final conformations and cavity sizes of the resulting assemblies. Towards this goal, we have developed a wide range of different organometallic architectures by rationally designing metal-containing precursors and organic ligands. In this Account, we present our recent work, focusing on half-sandwich iridium- and rhodium-based organometallic assemblies that we obtained through rational design. We discuss their synthesis, structures, and applications for the encapsulation of guests and enzyme-mimicking catalysis. We first describe a series of self-assembled organometallic metallarectangles and metallacages, which we constructed from preorganized dinuclear half-sandwich molecular clips and suitable pyridyl ligands. We extended this strategy to tune the size of the obtained rectangles, creating large cavities by introduction of larger molecular clips. The cavity was found to exhibit selective and reversible CH2Cl2 adsorption properties while retaining single crystallinity. By using suitable molecular clips, we found we could use a number of metallacycles as organometallic templates to direct photochemical [2 + 2] cycloaddition reactions, even in the solid state. Due to their chemical stability and potential applications in catalytic reactions, researchers are giving significant attention to complexes with cyclometalated backbones. We also highlight our efforts to develop efficient approaches to utilize cyclometalated building blocks for the formation of organometallic assemblies. By incorporation of imine ligands or benzoic acids, bipyridine linking subunits, and half-sandwich iridium or rhodium fragments, we built up a series of cationic and neutral metallacycles through cyclometalation-driven self-assembly. In addition, we have developed an efficient route to carborane-based metallacycles, involving the exploitation of metal-induced B-H activation. The method can provide prism-like metallacages, which are efficient hosts for the recognition of planar aromatic guests. This effort provides ...

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Anion‐Templated Assembly of Half‐Sandwich Rhodium‐Based Multinuclear Metallamacrocycles

Cited by 24 publications

References 101 publications

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

Half-sandwich rhodium and iridium fragments and carboxylate ligands as building blocks for the formation of metallamacrocycles

Half-Sandwich Iridium- and Rhodium-based Organometallic Architectures: Rational Design, Synthesis, Characterization, and Applications

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