Coordination-driven assembly of a supramolecular square and oxidation to a tetra-ligand radical species

Herasymchuk, Khrystyna; Miller, Jessica J.; MacNeil, Gregory A.; Sergeenko, Ania S.; McKearney, Declan; Goeb, Sébastien; Sallé, Marc; Leznoff, Daniel B.; Storr, Tim

doi:10.1039/c9cc02320h

Cited by 7 publications

(23 citation statements)

References 50 publications

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“…[9][10][11] The way has already been partially paved by research on coordination-driven self-assembly 12 although supramolecular architectures regulated by redox-active units have been considerably less investigated. [13][14][15] Polyoxometalates (POMs) are anionic oxo-clusters that display unique redox properties and are thoroughly investigated for their promising technological applications. [16][17][18] They can be functionalized into organic-inorganic hybrids though the covalent grafting of organometallic fragment onto the polyoxometalate framework.…”

Section: Introductionmentioning

confidence: 99%

Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions

et al. 2020

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The design and synthesis of a supramolecular square composed of polyoxometalate-based hybrid donors and ethylenediamine palladium(II) nodes are reported. The structure of the metallomacrocycle scaffold was inferred by diffusion NMR, small-angle X-ray scattering (SAXS), and molecular modeling. The metallomacrocycle scaffold that contains negatively and positively charged subunits can further self-assemble owing to a competition between the solvation energy of the discrete species and intermolecular electrostatic interactions. When the dissociating character of the solvent was lowered or when in the presence of a protic solvent, different types of multiscale organizations (vesicles and pseudo-1D structures) were selectively formed and were characterized by SAXS and transmission electron microscopy.

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Section: Introductionmentioning

confidence: 99%

Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions

et al. 2020

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“…However, the instability of metallacycle 3 during redox analysis was responsible to the irreversible part. [ 38 ]…”

Section: Resultsmentioning

confidence: 99%

“…Deuterated solvents were purchased from Energy Chemical Reagent Company. Bis‐pyridyl nickel salen metalloligand 1 [ 38 ] and platinum(II) acceptor 2 [ 26 ] were prepared according to the literature procedures. All air‐sensitive reactions were carried out under inert N 2 atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Supramolecular Polymer Networks with Enhanced Mechanical Properties: The Marriage of Covalent Polymer and Metallacycle^†

Zhang

Chen

et al. 2021

Chin. J. Chem.

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Main observation and conclusion Supramolecular polymer networks (SPNs) have always been the focus of research due to their novel features of good processability, stimuli‐responsiveness, self‐healing, and recyclability. Herein, we report the preparation of a metallacycle‐linked supramolecular gel via orthogonal metal‐ligand interactions and host‐guest interactions. A triangular metallacycle with three appended 21‐crown‐7 (21C7) units was obtained by the metal coordination of nickel(II)‐salen‐based dipyridyl ligands and platinum(II) acceptors. The integration of this metallacycle and traditional copolymer bearing secondary ammonium salts constructed a SPN via host‐guest recognition between 21C7 units and ammonium salts, and a supramolecular gel further formed at high concentration. Multiple stimulus responsiveness and self‐healing properties of gel were observed. The gel exhibited better stretchability compared to relative gel formed by copolymer alone owing to the synergistic effect of covalent bonds and supramolecular interactions. Moreover, compared to the model gel without metallacycles, the gel showed higher storage and loss moduli, and exhibited stronger stiffness in the self‐healing tests performed with rheometer, indicating the metallacycle played an important role in improving the stiffness and self‐healing of the gel. Therefore, the feasible approach to the formation of SPNs by the marriage of covalent polymers and metallacycles is expected to open a new way to design novel SPNs.

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“…Storr and co‐workers reported an ionic tetranuclear Pd(II) based molecular square [ 24 ] 8+ containing four Ni(II)‐saline spacers (L 24 ) [54] . The authors demonstrated that how the coordination of pyridyl unit of metalloligand to Pd(II) metal center influences the locus of oxidation in the complex.…”

Section: Metal Complex Spacer Based Ligands and Its Sccsmentioning

confidence: 99%

Emerging Spacers‐Based Ligands for Supramolecular Coordination Complexes

Mishra

Bhol

Kalimuthu

et al. 2021

The Chemical Record

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The design and self‐assembly of supramolecular coordination complexes (SCCs) i. e., discrete cyclic metalloarchitectures such as cycles, cages, mesocates, and helicates with desired size, shape, and properties have been increasing exponentially owing to their potential applications in molecular sensors, molecular cargos, molecular recognition, and catalysis. The introduction of the organic motifs and metal complexes as a spacer provides functionality to the metalloarchitecture. This review mainly focusses on newly evolving spacer based ligands employed to yield simple to high‐order metallosupramolecular assemblies using straight‐forward approaches. The new spacers including corannulene, organic cyclic framework, bicyclic organic motifs, aliphatic chain, metalloligands, triarylboron, BODIPY, azaphosphatrane, phosphine, and thio/selenophosphates offer a great set of properties and in‐built functionalities to the metalloarchitectures which are discussed in this review.

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Coordination-driven assembly of a supramolecular square and oxidation to a tetra-ligand radical species

Abstract: The design and synthesis of a supramolecular square was achieved by coordination-driven assembly of redox-active nickel(ii) salen linkers and (ethylenediamine)palladium(ii) nodes.

Cited by 7 publications

References 50 publications

Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions

Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions

Supramolecular Polymer Networks with Enhanced Mechanical Properties: The Marriage of Covalent Polymer and Metallacycle^†

Emerging Spacers‐Based Ligands for Supramolecular Coordination Complexes

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Coordination-driven assembly of a supramolecular square and oxidation to a tetra-ligand radical species

Abstract: The design and synthesis of a supramolecular square was achieved by coordination-driven assembly of redox-active nickel(ii) salen linkers and (ethylenediamine)palladium(ii) nodes.

Cited by 7 publications

References 50 publications

Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions

Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions

Supramolecular Polymer Networks with Enhanced Mechanical Properties: The Marriage of Covalent Polymer and Metallacycle†

Emerging Spacers‐Based Ligands for Supramolecular Coordination Complexes

Contact Info

Product

Resources

About

Supramolecular Polymer Networks with Enhanced Mechanical Properties: The Marriage of Covalent Polymer and Metallacycle^†