Group 8 Metallomacrocycles – Synthesis, Characterization, and Stability

Ludlow, James M.; Guo, Zaihong; Schultz, Anthony; Sarkar, Rajarshi; Moorefield, Charles N.; Wesdemiotis, Chrys; Newkome, George R.

doi:10.1002/ejic.201500971

Cited by 16 publications

(10 citation statements)

References 43 publications

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“…Similar to many other ligand systems, {M (tpy) 2 } complex stability is strongly associated with the coordinating metal cations. According to literature [33], the binding affinity of terpyridine towards transition metals has the following order: Ru 2+ > Os 2+ > Fe 2+ > Zn 2+ > Cd 2+ . Both ruthenium and osmium form stable tpy complexes with a very slow ligand exchange rate at room temperature.…”

Section: Introductionmentioning

confidence: 99%

Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry

Wei

Shi

et al. 2019

Coordination Chemistry Reviews

195

121

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As an NNN-tridentate ligand, the 2,2':6',2"-terpyridine plays an important role in coordination chemistry. With three coordination sites and low LUMO, terpyridine and its derivatives are one of the typical Pincer ligand and/or non-innocent ligands in transition metal catalysis. Interesting catalytic reactivities have been obtained with these tpy-metal complexes targeting some challenging transformations, such as CC bond formation and hydrofunctionalization. On the other hand, terpyridine ligands can form "closed-shell" octahedral complexes, which provide a linear and stable linkage in supramolecular chemistry. Numerous supramolecular architectures have been achieved using modified terpyridine ligands including Sierpiński triangles, hexagonal gasket and supramolecular rosettes. This review presents a summary of recent progress regarding transition metal-terpyridine complexes with the focus on their applications in catalysis and supramolecular structure construction. Facile synthesis of terpyridine derivatives is also described. We hope this article can serve to provide some general perspectives of the terpyridine ligand and their applications in coordination chemistry.

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Section: Introductionmentioning

confidence: 99%

Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry

Wei

Shi

et al. 2019

Coordination Chemistry Reviews

195

121

View full text Add to dashboard Cite

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“…The metal ions adopted to construct large discrete structures through direct self-assembly, however, were mainly limited to three metal ions with highly reversible coordination, viz., Cd(II), Zn(II), and Fe(II) . Very few cases have expanded the scope to Ru(II) and Os(II) with simple geometry and low complexity either by tedious postassembly separation or under harsh reaction condition with low yields . Perhaps, the lack of other metal ions in tpy-based supramolecular chemistry is due to the variable self-assembly conditions and challenging characterization .…”

Section: Introductionmentioning

confidence: 99%

Introducing Seven Transition Metal Ions into Terpyridine-Based Supramolecules: Self-Assembly and Dynamic Ligand Exchange Study

et al. 2020

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In coordination-driven self-assembly, 2,2′:6′,2″-terpyridine (tpy) has gained extensive attention in constructing supramolecular architectures on the basis of ⟨tpy-M-tpy⟩ connectivity. In direct self-assembly of large discrete structures, however, the metal ions were mainly limited to Cd(II), Zn(II), and Fe(II) ions. Herein, we significantly broaden the spectrum of metal ions with seven divalent transition metal ions M(II) (M = Mn, Fe, Co, Ni, Cu, Zn, Cd) to assemble a series of supramolecular fractals. In particular, Mn(II), Co(II), Ni(II), and Cu(II) were reported for the first time to form such large and discrete structures with ⟨tpy-M-tpy⟩ connectivity. In addition, the structural stabilities of those supramolecules in the gas phase and the kinetics of the ligand exchange process in solution were investigated using mass spectrometry. Such a fundamental study gave the relative order of structural stability in the gas phase and revealed the inertness of coordination in solution depending on the metal ions. Those results would guide the future study in tpy-based supramolecular chemistry in terms of self-assembly, characterization, property, and application.

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“…The formation of terpyridine-based nanostructures is a consequence of both kinetic and thermodynamic control; studies show that kinetically dominated complexation increases in the order Cd 2+ < Zn 2+ < Fe 2+ < Os 2+ < Ru 2+ . 51 The latter forms stable coordinative bonds, in which thermodynamic control over the self-assembly process is essentially lost by the creation of an irreversible metal complex; whereas, the former provides more stable thermodynamic constructs. The interconversion between different thermodynamic and kinetic superstructures is only possible under appropriate external stimuli, such as concentration and temperature.…”

Section: ■ Introductionmentioning

confidence: 99%

Terpyridine-Based, Flexible Tripods: From a Highly Symmetric Nanosphere to Temperature-Dependent, Irreversible, 3D Isomeric Macromolecular Nanocages

Chakraborty¹,

Wang²,

Endres³

et al. 2017

J. Am. Chem. Soc.

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A three-dimensional, highly symmetric sphere-like nanocage was synthesized using a terpyridine (tpy)-based, flexible tris-dentate ligand and characterized by single crystal X-ray analysis. To introduce more rigidity, one of the tpy units of the tris-dentate ligand was preblocked by stable connectivity to form the corresponding Ru-dimer. The complexation between Ru-dimer and Fe demonstrates an unexpected temperature-dependent assembly between two irreversible isomeric 3D nanocages. Investigation of the coordination process and structural configurations of the metal-ligand framework, affected by the introduction of rigidity and in the presence of external stimuli (temperature), is reported.

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Group 8 Metallomacrocycles – Synthesis, Characterization, and Stability

Cited by 16 publications

References 43 publications

Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry

Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry

Introducing Seven Transition Metal Ions into Terpyridine-Based Supramolecules: Self-Assembly and Dynamic Ligand Exchange Study

Terpyridine-Based, Flexible Tripods: From a Highly Symmetric Nanosphere to Temperature-Dependent, Irreversible, 3D Isomeric Macromolecular Nanocages

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