Supramolecular Metallopolymers: From Linear Materials to Infinite Networks

Bentz, Kyle C.; Cohen, Seth M.

doi:10.1002/anie.201806912

Cited by 130 publications

(67 citation statements)

References 66 publications

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“…Metallopolymers (MPs) or metal-containing polymers are one of the main classes of polymers discovered in the 20th century. [34][35][36][37][38][39][40][41] Various locations of metal centers from main group metals to transition metals and lanthanides relative to the polymer backbone were described by Wolf as Type I, Type II or Type III ( Fig. 1), in which the metal center is either tethered to the polymer backbone by an organic linker, either covalently coupled to the backbone, or directly included in the polymer backbone, respectively.…”

Section: Introductionmentioning

confidence: 99%

Recent advances in metallopolymer-based drug delivery systems

et al. 2019

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Section: Introductionmentioning

confidence: 99%

Recent advances in metallopolymer-based drug delivery systems

et al. 2019

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“…disconnection of the M-L bonds, completely new synthetic conditions are required each time a new primary coordination sphere is sought. [4][5][6][7] Figure 1. (a) The pKa values (in DMSO) of a series of selective functional groups coordinating with metal ions through deprotonation are summarized here (the pKa values of carboxylic acid, amide, and amidine refer to that of benzoic acid and benzamide, and benzamidine, respectively).…”

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confidence: 99%

Metallopolymerization as a Strategy to Translate Ligand-Modulated Chemoselectivity to Porous Catalysts

et al. 2019

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Porous catalysts have garnered substantial interest as potential platforms for group-transfer catalysis due to the ability to site-isolate catalysts and to non-covalently colocalize substrates in proximity to reactive intermediates. In contrast to soluble molecular catalysts, the limited synthetic toolbox available to prepare porous catalysts presents a formidable challenge to controlling the primary coordination sphere of lattice-confined catalysts and thus modulating the electronic structures of reactive catalyst intermediates. Here, we utilize Sonogashira cross-coupling chemistry to prepare a family of porous metallopolymers, in which the primary coordination sphere of Ru2 sites is systematically varied. The newly synthesized materials are characterized by IR, elemental analysis, gas sorption, powder X-ray diffraction, thermogravimetric analysis, X-ray absorption spectroscopy, and diffuse-reflectance UV-vis-NIR spectroscopy. The resulting porous materials are catalysts for nitrene-transfer chemistry and the chemoselectivty for allylic amination of olefin aziridination can be tuned by modulating the primary coordination sphere of the catalyst sites. The demonstration of metallopolymerization as a rational synthetic strategy allows to translate ligand-modulated chemoselectivity to porous catalysts, which represents a new opportunity to tailor the functionality of heterogeneous analogues of molecular complexes.Introduction Synthesis of crystalline metal-organic frameworks (MOFs) is predicated on reversible metal-ligand (M-L) bond-forming chemistry which simultaneously assembles the porous network and establishes the primary coordination sphere of the lattice-confined transition metal ions. 1 The necessity for reversible M-L bond formation to achieving material crystallinity limits the diversity of ligands that can be utilized to generate potential catalyst MOFs. Pyridyl-, carboxylate-, and azolate-derived ligands ¾ all of which are fairly weak-field ligands with low-pKa conjugate acids ¾ are ubiquitous in the chemistry of MOFs. In contrast, strongly basic donors, such as amido, amidinate, and alkoxide ligands ¾ common ligands in molecular transition metal catalysts ¾ are rarely, if ever, encountered in the coordination chemistry of MOFs (Figure 1a). 2, 3 In addition, because the traditional synthetic logic of MOF chemistry is based on retrosynthetic

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“…As the structures of coordination polymers are strongly influenced by the organic ligands and metal ions [15,16,31], it is important to choose suitable ligands and metal ions under appropriate synthetic conditions in order to synthesize coordination complexes with interesting structures. The flexibility of the ligand is a key parameter to direct the assembly into polymers instead of frameworks [17].…”

Section: Fabrication Of Metal Coordination Polymersmentioning

confidence: 99%

Supramolecular Assembly of Benzimidazole Derivatives and Applications

Beloqui¹

2019

Chemistry and Applications of Benzimidazole and Its Derivatives

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Herein, we focus on the chemical and physical properties of benzimidazole and its derivatives used for the synthesis of supramolecular materials. The design and modification of benzimidazole opens the scope of the diversity of structures (different sizes and morphologies) that can be built. The synthesized materials include not only small coordination complexes but also isolated crystals, metal-organic frameworks, metal-coordination polymers, smart nanocontainers, and more advanced macrostructures such as microflowers and nanowires. These supramolecular structures are based on noncovalent interactions, mostly on metal coordination chemistry and π-π stacking interactions. Moreover, the same molecule, due to its chemical structure, can undergo both sorts of interactions in order to induce the self-assembly into supramolecular materials. In this process, as it is shown in this chapter, the conditions used for the assembly determine the final structure and morphology of the fabricated macromolecule. Finally, we show most recent applications of these materials in the field of sensing, photoluminescence, fuel cell, and fabrication of new nanostructures.

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Supramolecular Metallopolymers: From Linear Materials to Infinite Networks

Cited by 130 publications

References 66 publications

Recent advances in metallopolymer-based drug delivery systems

Recent advances in metallopolymer-based drug delivery systems

Metallopolymerization as a Strategy to Translate Ligand-Modulated Chemoselectivity to Porous Catalysts

Supramolecular Assembly of Benzimidazole Derivatives and Applications

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