Construction of Tetranuclear Macrocycles through CH Activation and Structural Transformation Induced by [2+2] Photocycloaddition Reaction

Yu, Wei‐Bin; Han, Ying‐Feng; Lin, Yue‐Jian; Jin, Guo‐Xin

doi:10.1002/chem.201002986

Cited by 67 publications

(16 citation statements)

References 59 publications

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“…127,128 Recently, the same group reported the synthesis of half-sandwich iridium metallarectangles induced by C–H activation. 129,130 Bimetallic edges, formed from half-sandwich iridium arene precursors and pyrazine or bispyridyl linkers, were converted to tetranuclear metallarectangles upon treatment with dicarboxylic acids such as fumaric acid, 1,3-benzenedicarboxylic acid, 5-amino-1,3-benzenedicarboxylic acid or azobenzene 4,4′-dicarboxylic acid. The Cp*Ir III fragment catalyzes the C–H activation of dicarboxylic acids to build the macrocyclic architectures.…”

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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“…38 These metallarectangles could also be prepared by the two-step synthetic pathway. 39,40 The structure of each complex has been confirmed by a single-crystal X-ray analysis. We have also extensively investigated the formation of metallarectangles through the C−H activation of fumaric acid.…”

Section: ■ C−h-activation-driven Self-assemblymentioning

confidence: 96%

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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“…2012年, Lu等 [40] 报道了以铼为金属中心的中性大图 5 (a) 7a的阳离子部分分子结构图; (b) 7a的两个双键的扭转角为89° [ 37] (网络版彩图) 图 6 化合物8的光化学反应示意图 [38] 图 7 化合物10a、、、10b的光化学反应示意图 [39] 环化合物 MacGillivray等 [42] 以银离子作为模板与带有末端烯烃的4-乙烯基吡啶作为配体自组装形成化合物16 (18). 该化合物图 8 化合物12a、12b、12c到13a、13b、13c的反应示意图 [40] 图 9 化合物14a~14c的结构示意图 [41] 图 10 化合物16的[2+2]光化学反应 [42] 在光照下通过…”

Section: 基于金属Re大环框架控制的[2+2]光化学反应unclassified

Template-directed photochemical [2+2] cycloaddition within discrete assemblies

Gan¹,

Zhang²,

Huo³

et al. 2017

Sci. Sin.-Chim

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The photochemical induced [2+2]cycloaddition reaction is one of the most powerful means for the syntheses of cyclobutane derivatives. However the highly efficient conversion of this reaction is relatively difficult. Recent studies show that the efficiency of this reaction could be promoted by discrete assemblies in solid or crystal state. In this review, we summarized the recent progress of the assemblies-assisted photochemical [2+2]cycloaddition reactions and previewed it development prospect.

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Construction of Tetranuclear Macrocycles through CH Activation and Structural Transformation Induced by [2+2] Photocycloaddition Reaction

Cited by 67 publications

References 59 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 Iridium- and Rhodium-based Organometallic Architectures: Rational Design, Synthesis, Characterization, and Applications

Template-directed photochemical [2+2] cycloaddition within discrete assemblies

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