Synthesis, crystal structure and electronic properties of [3.3]metaparacyclophane-bridged bimetallic ruthenium alkynyl complexes

Wang, Xiaoxiao; You, Xiaoxiao; Shang, Zhi-Liang; Xia, Jianlong

doi:10.1016/j.jorganchem.2015.12.008

Cited by 6 publications

(3 citation statements)

References 52 publications

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“…Here, like the previous example, the oxidation was largely localized on the bridging ligands, with a dominant contribution from the benzodithiophene core . Similar types of [3,3]metaparacyclophanes bridged bimetallic Ru-complexes have been reported showing intramolecular edge-to-face interactions, both in solutions and in the solid state . In addition to the above-discussed examples, numerous other redox-active Ru-based complexes are reported in literature with unique properties and applications.…”

Section: Structure–property Relationshipssupporting

confidence: 72%

“…338 Similar types of [3,3]metaparacyclophanes bridged bimetallic Ru-complexes have been reported showing intramolecular edge-to-face interactions, both in solutions and in the solid state. 339 In addition to the above-discussed examples, numerous other redox-active Ru-based complexes are reported in literature with unique properties and applications. Researchers studied the impact of inclusion of organo phosphonate substituent at the termini 340 or electro-active tetrathia-fulvalene 341 on the electronic communication and also reported distance-dependent electronic coupling in wire-like poly-yne-diyls.…”

Section: Chemical Reviewsmentioning

confidence: 99%

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Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

et al. 2018

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Conjugated poly-ynes and poly(metalla-ynes) constitute an important class of new materials with potential application in various domains of science. The key factors responsible for the diverse usage of these materials is their intriguing and tunable chemical and photophysical properties. This review highlights fascinating advances made in the field of conjugated organic poly-ynes and poly(metalla-ynes) incorporating group 4-11 metals. This includes several important aspects of conjugated poly-ynes viz. synthetic protocols, bonding, electronic structure, nature of luminescence, structure-property relationships, diverse applications, and concluding remarks. Furthermore, we delineated the future directions and challenges in this particular area of research.

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Section: Structure–property Relationshipssupporting

confidence: 72%

Section: Chemical Reviewsmentioning

confidence: 99%

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

et al. 2018

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“…In many MV and related studies, density functional theory (DFT) calculations have been proven useful in predicting the spin distributions of molecular materials in different redox states. 17 In the beginning, we performed the DFT calculations of the one-electron oxidized forms 4 2+ – 9 2+ with the commonly used UB3LYP hybrid functional. 18 The spin density distributions are displayed in the left column of Figure 8.…”

Section: Resultsmentioning

confidence: 99%

Substituent Effects on the Electrochemistry and Electronic Coupling of Terphenyl-Bridged Cyclometalated Ruthenium–Amine Conjugated Complexes

Shen

Shao

et al. 2018

ACS Omega

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Six terphenyl-bridged cyclometalated ruthenium–amine conjugated complexes 4 (PF 6 )– 9 (PF 6 ) were synthesized and studied. Three different substituents, methoxy, methyl, and chloro, were used to vary the electronic nature of the amine unit, and two terminal ligands 2,2′:6′,2″-terpyridine (tpy) and trimethyl-4,4′,4″-tricarboxylate-2,2′:6′,2″-terpyridine (Me 3 tctpy) were used to tune the electronic nature of the ruthenium component. All complexes, except 7 (PF 6 ) with the methoxy substituent and Me 3 tctpy ligand, display two well-separated redox waves in the potential range of +0.5 to +1.1 V versus Ag/AgCl. The regular electrochemical changes of these complexes help to establish the oxidation order of ruthenium and amine and hence of the direction of the electron transfer in odd-electron state. The degree of electronic coupling was estimated by analyzing the donor-to-acceptor charge transfer band in the near-infrared region obtained by oxidative spectroelectrochemical measurements. Electron paramagnetic resonance analyses and density functional theory calculations were performed on the one-electron oxidized forms to obtain information on the spin distribution of these complexes.

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Metal‐to‐Metal Distance Modulation by Ligand Design: A Case Study of Structure‐Property Correlation in Planar Chiral Cyclophanyl Metal Complexes

Hassan

Bräse

2021

Chemistry A European J

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Multinuclear metal complexes have seen tremendous progress in synthetic advances, their versatile structural features, and emerging applications. Here, we conceptualize Metal-to-Metal distance modulation in cyclophanyl metal complexes by bridging ligand design employing the cofacially stacked cyclophanyl-derived pseudo-geminal, -ortho, -meta, and -para constitutional isomers grafted with N-, O-, and P-containing chelates that allow the installation of diverse (hetero)metallic moieties in a distance-defined and spatially-oriented relation to one another. Metal-to-Metal distance modulation and innate transannular "through-space" π-π electronic interactions via the co-facially stacked benzene rings in cyclophanyl-derived complexes as well as their specific stereochemical structural features (element of planar chirality) are crucial factors that contribute to the tuning of structure-property relationships, which stand at the very center from the perspective of cooperative effects in catalysis as well as emerging material applications.

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Synthesis, crystal structure and electronic properties of [3.3]metaparacyclophane-bridged bimetallic ruthenium alkynyl complexes

Cited by 6 publications

References 52 publications

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

Rise of Conjugated Poly-ynes and Poly(Metalla-ynes): From Design Through Synthesis to Structure–Property Relationships and Applications

Substituent Effects on the Electrochemistry and Electronic Coupling of Terphenyl-Bridged Cyclometalated Ruthenium–Amine Conjugated Complexes

Metal‐to‐Metal Distance Modulation by Ligand Design: A Case Study of Structure‐Property Correlation in Planar Chiral Cyclophanyl Metal Complexes

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