Structural and Electronic Variations of sp/sp<sup>2</sup> Carbon-Based Bridges in Di- and Trinuclear Redox-Active Iron Complexes Bearing Fe(diphosphine)<sub>2</sub>X (X = I, NCS) Moieties

Lissel, Franziska; Blacque, Olivier; Venkatesan, Koushik; Berke, Heinz

doi:10.1021/om500602m

Cited by 10 publications

(2 citation statements)

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“…The extrapolation of lowest electron excitation energy for trans-[Fe(cyclam) (C 2n R) 2 ] + gives a value of 1.44 eV as n → ∞. Berke and co-workers 329 found that the E g and chemical hardness of redox-active acetylide complexes could be modified by changing the sp/sp 2 bridging ligand. They reported several new intrinsically functional and redoxactive complexes with iodo and isothiocyanate as terminal groups (163,Chart 15), which are especially suitable for the electronics industry.…”

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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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: 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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“…For example, Lapinte and Lo Sterzo and their respective co‐workers have reported that 2,5‐diethynylthiophene‐linked Fe(dppe)Cp* and Fe(dppe)Cp [Cp = cyclopentadienyl, Cp* = pentamethylpentadienyl, dppe = 1,2‐bis(diphenylphosphino)ethane] termini are more strongly coupled than the 1,4‐diethynylbenzene‐bridged analogues , . Many other bimetallic complexes and metallopolymers with 2,5‐diethynylthiophene‐based bridging ligands are also known to offer highly delocalised electronic structures with significant contributions from the bridging ligand to the frontier molecular orbitals , , , …”

Section: Introductionmentioning

confidence: 99%

Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te

et al. 2017

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An homologous series of divinylchalcogenophene‐bridged binuclear ruthenium complexes [{(PMe3)3Cl(CO)Ru}2(µ‐CH=CH‐C4H2E‐CH=CH)] (4a–4d, E = O, S, Se, Te) have been synthesised and fully characterised by X‐ray crystallography and various spectroscopic techniques. The single‐crystal X‐ray diffraction results reveal a distinct short/long bond‐length alternation along the polyene‐like hydrocarbon backbone, with geometric constraints imposed by the chalcogenophene leading to an increasing distance between the two metal centres (dRu–Ru) in complexes 4a–4d as the heteroatom in the five‐membered ring is changed from oxygen (9.980 Å in 4a) to tellurium (11.063 Å in 4d). The complexes undergo two sequential one‐electron oxidation processes, the half‐wave potential and separation of which appear to be sensitive to a range of factors, including aromatic stabilisation and re‐organisation energies. Analysis of [4a–4d]n+ (n = 0, 1, 2) by UV/Vis/NIR and IR spectroelectrochemical methods, supported by DFT calculations (n = 0, 1), revealed that the redox character of the complexes is dominated by the polyene‐like backbone with the chalcogenide playing a subtle but influential, structural rather than electronic, role. In the radical cations [4a–4d]+, the charge is rather effectively delocalised over the 10‐atom Ru–[4‐s‐cis‐all‐trans‐(CH=CH)4]–Ru chain, giving rise to a species with spectroscopic properties not dissimilar to oxidised polyaceylene.

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Electronic Interactions between Ferrocenyl Units Facilitated by the Cobalt Bis(dicarbollide) Anion Linker: An Experimental and DFT Study

et al. 2018

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The electronic interaction between two terminal ferrocenyl units connected by the cobalt bis(dicarbollide) anion linker was investigated. The bis(ferrocenylethynyl)cobalt bis(dicarbollide) anion (3) linking the two ferrocenyl units with the cobalt bis(dicarbollide) anion was synthesized by the reaction of a zinc derivative of ethynylferrocene with the diiodocobalt bis(dicarbollide) anion using Pd0 catalyst in 75 % yield. Complex 3 was unambiguously characterized by NMR and IR spectroscopy, mass spectrometry, and single‐crystal X‐ray crystallography. The X‐ray structure of 3 reveals that the two ferrocenyl units are perpendicular to each other with a total distance of 1.86 nm between the two Fe metal centers. The cyclic voltammogram of 3 shows a single oxidation potential corresponding to the two ferrocenyl units. Time‐dependent density functional theory (TD‐DFT) studies on complex 3 in tandem with UV/Vis spectroscopic analysis indicate the dominance of the dicarbollide moiety in the LUMOs, and HOMO→LUMO transitions at 435 nm illustrate the charge transfer from the two ferrocenyl units to the cobalt bis(dicarbollide) linker.

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Structural and Electronic Variations of sp/sp² Carbon-Based Bridges in Di- and Trinuclear Redox-Active Iron Complexes Bearing Fe(diphosphine)₂X (X = I, NCS) Moieties

Abstract: Starting from the mononuclear precursor transFe(depe) 2 I 2 (depe = 1,2-bis(diethylphosphino)ethane), four dinuclear complexes IFe(depe) 2 −R−Fe(depe) 2

Cited by 10 publications

References 68 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

Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te

Electronic Interactions between Ferrocenyl Units Facilitated by the Cobalt Bis(dicarbollide) Anion Linker: An Experimental and DFT Study

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Structural and Electronic Variations of sp/sp2 Carbon-Based Bridges in Di- and Trinuclear Redox-Active Iron Complexes Bearing Fe(diphosphine)2X (X = I, NCS) Moieties

Abstract: Starting from the mononuclear precursor transFe(depe) 2 I 2 (depe = 1,2-bis(diethylphosphino)ethane), four dinuclear complexes IFe(depe) 2 −R−Fe(depe) 2

Cited by 10 publications

References 68 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

Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te

Electronic Interactions between Ferrocenyl Units Facilitated by the Cobalt Bis(dicarbollide) Anion Linker: An Experimental and DFT Study

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Structural and Electronic Variations of sp/sp² Carbon-Based Bridges in Di- and Trinuclear Redox-Active Iron Complexes Bearing Fe(diphosphine)₂X (X = I, NCS) Moieties