Linear bilateral extended 2,2′:6′,2′′-terpyridine ligands, their coordination complexes and heterometallic supramolecular networks

Veliks, Janis; Tseng, Jui-Chang; Arias, Karla I.; Weisshar, Florian; Linden, Anthony; Siegel, Jay S.

doi:10.1039/c4sc01025f

Cited by 16 publications

(25 citation statements)

References 91 publications

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“…Interestingly, terpyridine metal complexes [M(Tpy) 2 n+ ] usually possess a distorted octahedral coordination geometry, caused by hexacoordinate metal ions, where a linear bilateral conformation of ligands can be obtained by complexation of terpyridine ligands to a metal center in 2:1 ratio . The directionality of these non‐covalent bonds is crucial in the design and construction of supramolecular systems, either presenting flexible and rigid polymer‐like conformation or geometrically well‐defined architectures.…”

Section: Introductionmentioning

confidence: 99%

Divergent Terpyridine‐Based Coordination for the Construction of Photoactive Supramolecular Structures

2019

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Exploring new materials to manipulate luminescent radiation and investigate the interaction of light and matter is one of the most compelling prospects of our century. Supramolecular chemistry has unraveled the opportunity to synergistically combine the chemical and optoelectronic properties of the most diverse classes of compounds. Among these, terpyridines have acted as pivotal ligand units that enable selfassembly of multicomponent chromophoric systems. In this review we therefore elucidate the metal-coordinating ability of [a]

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Section: Introductionmentioning

confidence: 99%

Divergent Terpyridine‐Based Coordination for the Construction of Photoactive Supramolecular Structures

2019

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“…In chemical synthesis, selfassembled macromolecular architectures attract attention due to the advanced properties of the organized entities. 1,2 One of the challenges of macromolecular assemblies is their rigorous characterisation due to their large size and extended connectivity. NMR, UV-Vis and X-ray have traditionally been applied to characterise complexes and their properties.…”

Section: Introduction (Bio)macromolecular Assembliesmentioning

confidence: 99%

Nitroxide–nitroxide and nitroxide–metal distance measurements in transition metal complexes with two or three paramagnetic centres give access to thermodynamic and kinetic stabilities

Giannoulis

Ackermann

Spindler

et al. 2018

Phys. Chem. Chem. Phys.

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Fundamentally, the stability of coordination complexes and of templated (bio)macromolecular assemblies depends on the thermodynamic and kinetic properties of the intermediates and final complexes formed. Here, we used pulse EPR (electron paramagnetic resonance) spectroscopy to determine the stabilities of nanoscopic assemblies formed between one or two nitroxide spin-labelled tridentate 2,2':6',2''-terpyridine (tpy) ligands and divalent metal ions (FeII, ZnII, CoII and CuII). In three distinct approaches we exploited (a) the modulation depth of pulsed electron-electron double resonance (PELDOR) experiments in samples with increasing metal-to-ligand ratios, (b) the frequencies of PELDOR under broadband excitation using shaped pulses and (c) the distances recovered from well-resolved PELDOR data in fully deuterated solvents measured at 34 GHz. The results demonstrate that PELDOR is highly sensitive to resolving the stability of templated dimers and allows to readily distinguish anti-cooperative binding (for CuII ions) from cooperative binding (for CoII or FeII ions). In the case of paramagnetic ions (CoII and CuII) the use of broadband PELDOR allowed to identify the cooperativity of binding from the time domain and distance data. By using a second labelled tpy ligand and by mixing two homoleptic complexes of the same metal centre we could probe the kinetic stability on a timescale of tens of seconds. Here, tpy complexes of CuII and ZnII were found to be substitutionally labile, CoII showed very slow exchange and FeII was inert under our conditions. Not only do our chemical models allow studying metal-ligand interactions via PELDOR spectroscopy, the design of our study is directly transferable to (bio)macromolecular systems for determining the kinetic and thermodynamic stabilities underpinning (templated) multimerisation. Considering the limited methods available to obtain direct information on the composition and stability of complex assemblies we believe our approach to be a valuable addition to the armoury of methods currently used to study these systems.

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“…5, 6 Recently, bilateral extended terpy ligands [2,6-bis-(2-substituted furo[2,3-c]pyridin-5-yl)pyridine] have appeared as a new class of building blocks in supramolecular chemistry. 7 These octahedral metal complexes of tridentate terpy fused with five-membered furan rings mimic the crossing topology normally associated with tetrahedral metal complexes of bidentate 5,5′-functionalized 2,2′-bipyridine (bipy; Figure 1). Such directional metal complexes are potential building blocks for the assembly of heterometallic coordination polymers and metal−organic frameworks (MOFs).…”

Section: ■ Introductionmentioning

confidence: 96%

Three Steps in One Pot: Synthesis of Linear Bilateral Extended 2,2′:6′,2″-Terpyridineruthenium(II) Complexes

2014

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Metal complexes of linear bilateral extended 2,2':6',2″-terpyridine [2,6-bis(2-substituted furo[2,3-c]pyridin-5-yl)pyridine] are topological tridentate analogues of 5,5'-functionalized 2,2'-bipyridine. The present methodology provides access to linear bilateral extended 2,2':6',2″-terpyridineruthenium(II) complexes starting from 5,5″-bis(methoxymethoxy)-4,4″-bis(substituted ethynyl)-2,2':6',2″-terpyridines via one-pot cleavage of the methoxymethyl (MOM) protecting group, cycloisomerization, and metal complexation in the presence of Ru(DMSO)4Cl2. In this reaction, ruthenium(II) likely plays a triple role, acting as a Lewis acid to cleave the MOM ether, a catalyst facilitating 5-endo-dig cyclization, and a coordination metal center, being an integral part of the final product.

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Linear bilateral extended 2,2′:6′,2′′-terpyridine ligands, their coordination complexes and heterometallic supramolecular networks

Abstract: Combination of five- and six-membered rings allows creation of 2,2′:6′,2′′-terpyridine derivatives mimicking the topology of 5,5′-functionalized 2,2′-bipyridine. This molecular design led to the assembly of heterometallic supramolecular networks.

Cited by 16 publications

References 91 publications

Divergent Terpyridine‐Based Coordination for the Construction of Photoactive Supramolecular Structures

Divergent Terpyridine‐Based Coordination for the Construction of Photoactive Supramolecular Structures

Nitroxide–nitroxide and nitroxide–metal distance measurements in transition metal complexes with two or three paramagnetic centres give access to thermodynamic and kinetic stabilities

Three Steps in One Pot: Synthesis of Linear Bilateral Extended 2,2′:6′,2″-Terpyridineruthenium(II) Complexes

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