The molecular electrochemistry of metal–organic metallamacrocycles

Winter, Rainer F.

doi:10.1016/j.coelec.2017.11.011

Cited by 18 publications

(11 citation statements)

References 52 publications

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“…1 H NMR (400 MHz, CDCl 3 ): δ (ppm) 7.76 (s, 2H, H (3) ), 2.39 (s, 3H, H (8) ), 1.29 (s, 9H, H (6) ). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ (ppm) 167.7 (s, C (7) ), 152.9 (s, C (4) ), 149.3 (s, C (1) ), 137.0 (s, C (3) ), 90.2 (s, C (2) ), 34.6 (s, C (5) ), 31.3 (s, C (6) ), 21.5 (s, C (8) ).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Even though the majority of these compounds contain redox-active metal nodes or bridging ligands, their electrochemical properties have long remained less well explored and underutilized. , There is, however, a rapidly growing number of studies on this topic, as the redox activity of such structures can potentially lead to additional functional properties. Some work has been directed toward the incorporation of ferrocene units into macrocyclic structures, either as peripherically attached, redox-active pendants or as integral parts of the linkers .…”

Section: Introductionmentioning

confidence: 99%

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Self-Assembled Redox-Active Tetraruthenium Macrocycles with Large Intracyclic Cavities

et al. 2020

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We report on five tetranuclear metallamacrocycles with particularly large inner voids of up to 19.4 × 18.9 Å. The macrocyclic complexes were obtained by the self-assembly of spatially extended organic dicarboxylate linkers with two different dinuclear bis(alkenyl) diruthenium precursors. The five complexes include one pair of constitutional isomers, complexes 2-NB and 2-BN, which differ with respect to whether the incorporated triarylamine functionality is part of the "conductive" π-conjugated (2-NB) or the insulating dicarboxylate linkers (2-BN). All macrocyclic complexes were characterized by NMR spectroscopy, UHR ESI mass spectrometry, cyclic and square wave voltammetry, and in two instances by X-ray diffraction studies on single crystals. We also investigated the properties of their various oxidized forms via IR/NIR and UV/vis/NIR spectroelectrochemistry as well as by EPR spectroscopy. DFT studies provide further insight into the structural and electronic properties of these compounds.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Self-Assembled Redox-Active Tetraruthenium Macrocycles with Large Intracyclic Cavities

et al. 2020

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“…We have recently reported on some representatives of new types of metallamacrocyclic ruthenium complexes based on alkenylarylene and carboxylate linkers [1][2][3][4], which add to the rapidly growing class of redox-active metallamacrocycles [5][6][7]. Metallacycles of type I in Figure 1 are constructed from bis(alkenyl)arylene diruthenium complexes and isophthalic acid derivatives or pyridine-3,5-dicarboxylate as two different kinds of building blocks [1,2,4].…”

Section: Introductionmentioning

confidence: 99%

Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities

et al. 2018

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We present four new tetraruthenium macrocycles built from two 1,4-divinylphenylene diruthenium and two isophthalic acid building blocks with peripheral, potentially mono- or tridentate donor functions attached to the isophthalic linkers. These macrocycles are characterized by multinuclear NMR spectroscopy, mass spectrometry and, in the case of the thioacetyl-appended complex 4, by X-ray crystallography. Cyclic and square wave voltammetry establish that the macrocycles can be oxidized in four consecutive redox steps that come as two pairs of two closely spaced one-electron waves. Spectroscopic changes observed during IR and UV/Vis/NIR spectroelectrochemical experiments (NIR = near infrared) show that the isophthalate linkers insulate the electroactive divinylphenylene diruthenium moieties against each other. The macrocycles exhibit nevertheless pronounced polyelectrochromism with highly intense absorptions in the Vis (2+/4+ states) and the NIR (2+ states) with extinction coefficients of up to >100,000 M−1·cm−1. The strong absorptivity enhancement with respect to the individual divinylphenylene diruthenium building blocks is attributed to conformational restrictions imposed by the macrocycle backbone. Moreover, the di- and tetracations of these macrocycles are paramagnetic as revealed by EPR spectroscopy.

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“…They mainly concern a redox modulation led on the guest itself 47,48 rather than a redox reaction affecting the ionic charge of the host cavity. In addition, and despite an always increasing number of electroactive metalla-cages, [49][50][51][52][53][54][55][56] only few of them involve a redox-active cavity and moreover their constituting ligands are mostly based on electron-deficient frameworks such as triazine [57][58][59] , perylene diimide, [60][61][62][63] or naphthalene diimide. 64 Some can be oxidized, 65 but their electron-activity is most often localized on the outside of the cage cavity with pendant covalently linked redox-active groups, 66 rather than centered on the cavity.…”

Section: Introductionmentioning

confidence: 99%

Electron-rich Coordination Receptors Based on Tetrathiafulvalene Derivatives: Controlling the Host–Guest Binding

Goeb

Sallé

2021

Acc. Chem. Res.

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CONSPECTUS.The coordination-driven self-assembly methodology has emerged over the last decades as an extraordinary versatile synthetic tool for obtaining discrete macrocyclic or cage structures. Rational approaches using wide libraries of ligands and metal complexes have allowed to reach more and more sophisticated discrete structures such as interlocked, chiral or heteroleptic cages, and some of them are designed for guest binding applications. Efforts have been notably produced in controlling host-guest affinity with in particular, an evident interest for targeting substrate transportation and subsequent delivering. Recent accomplishments in this direction were described from functional cages which can be addressed with light, pH or through a chemical exchange. The case of a redox-stimulation has been much less explored. In this case, the charge state of the redox-active cavity can be controlled through an applied electrical potential or introduction of an appropriate oxidizing/reducing chemical agent. Beyond possible applications in electrochemical sensing for environmental and medical sciences as well as for redox catalysis, controlling the cavity charge offers the possibility to modulate the host-guest binding affinity KEY REFERENCES

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The molecular electrochemistry of metal–organic metallamacrocycles

Cited by 18 publications

References 52 publications

Self-Assembled Redox-Active Tetraruthenium Macrocycles with Large Intracyclic Cavities

Self-Assembled Redox-Active Tetraruthenium Macrocycles with Large Intracyclic Cavities

Tetraruthenium Metallamacrocycles with Potentially Coordinating Appended Functionalities

Electron-rich Coordination Receptors Based on Tetrathiafulvalene Derivatives: Controlling the Host–Guest Binding

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