Synthesis and electronic structure of rigid rod octahedral Ru-σ-acetylide complexes

Khan, Muhammad S.; Kakkar, Ashok; Ingham, Scott L.; Raithby, Paul R.; Lewis, Jack; Spencer, Brock; Wittmann, Felix; Friend, Richard H.

doi:10.1016/0022-328x(94)80211-4

Cited by 68 publications

(28 citation statements)

References 23 publications

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“…Recent studies of the bonding in metal alkynyl, butadiynyl, and bis(alkynyl) complexes, based on photoelectron spectroscopic studies and/or molecular orbital calculations, ,− support previous calculational findings which indicate that there is considerable mixing of the filled metal d orbitals with the filled π-system of the alkynyl moiety. The energy mismatch between the metal d-levels and alkynyl π*-levels, at least in cases in which there are no strong π-acceptor substituents in conjugation with the alkynyl moiety, leads to a lack of significant π-backbonding.…”

Section: Iii12 Structural Studies and Bonding In The M−c⋮c Fragmentsupporting

confidence: 64%

“…More recently, Lewis et al have utilized a convenient metathesis reaction involving trimethyl tin reagents, reported earlier by Lappert and co-workers, to yield poly-ynes containing group 8, − 9, , and 10 190-193 metals. The polymers were prepared by reacting an equimolar amount of bis-trimethylstannyl acetylides and the appropiate metal halide complexes in the presence of CuI as a catalyst (Scheme ).…”

Section: Rigid-rod Organometallic Polymersmentioning

confidence: 99%

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Organometallic Polymers with Transition Metals in the Main Chain

1999

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Section: Iii12 Structural Studies and Bonding In The M−c⋮c Fragmentsupporting

confidence: 64%

Section: Rigid-rod Organometallic Polymersmentioning

confidence: 99%

Organometallic Polymers with Transition Metals in the Main Chain

1999

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“…[24,25] The corresponding band in 7 is bathochromically shifted to 26380 cm -1 (379 nm) along with a hyperchromic shift (ε = 11.5 ϫ 10 4 m -1 cm -1 ). For both 4 and 7, the absorptivity is slightly greater than in the corresponding chloro analogues 3 (348 nm, 3.8 ϫ 10 4 m -1 cm -1 ) and 6 (373 nm, 7.8 ϫ 10 4 m -1 cm -1 ).…”

Section: Resultsmentioning

confidence: 99%

Multistate Redox‐Active Metalated Triarylamines

et al. 2011

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International audiencetrans-[(η5-C5H5)Fe(η5-C5H4-η1-C≡C)Ru(C≡C-4-C6H4NPh2)(dppe)2] [4; dppe = 1,2-bis(diphenylphosphanyl)ethane] and trans,trans,trans-[₍η5-C5H5)Fe(η5-C5H4-η1-C≡C)Ru(dppe)2(C≡C-4-C6H4)₃N] (7) have been synthesized from trans-[Ru(C≡C-4-C6H4NPh2)Cl(dppe)2] (3) and trans,trans,trans-[₍dppe)2ClRu(C≡C-4-C6H4)₃N] (6), respectively, and the identities of trans-[Ru(C=CH-4-C6H4NPh2)Cl(dppe)2][PF6] (2, precursor to 3), 3, and 4 have been confirmed crystallographically. Chemical oxidation of 4 and 7 afforded the isolable mixed-valence species 4[PF6] and 7[PF6]3. The CV of 4 reveals sequential loss of three electrons in fully reversible oxidation steps, whereas the CV of 7 shows five reversible redox waves; in contrast, oxidation of the precursor amines HC≡C-4-C6H4NPh2 and (HC≡C-4-C6H4)3N are irreversible processes. All oxidation processes afford reversible changes in the linear optical properties. Complementary time-dependent density functional theory (TD-DFT) studies suggest that the initial oxidation process for 4 and 7 is iron-centered and is followed by one (for 4) or three (for 7) ruthenium-centered oxidations. The final reversible oxidation is assigned by TD-DFT as delocalized along the metalla-ethynylarylamine moiety. The intense optical changes consequent on reversible oxidation, together with their charge-transfer character, suggest that 4 and 7 have potential as nonlinear as well as linear optical multistate switches

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“…262 However, Vacher et al 261 reported very little effect of the auxiliary ligand or the isomerism on the frequency of the ν CC stretching vibration in Pt(II)-acetylides. Prior to this, Lewis et al 263 noted that the attachment of PBu 3 to a Ru-metal fragment shifts the ν M−C stretching frequency to the higher values compared to complex containing PH 3 . Furthermore, the replacement of a group 10 (d 8 ) metal or by a group 8 (d 6 ) metal lowers the stretching frequency.…”

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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Synthesis and electronic structure of rigid rod octahedral Ru-σ-acetylide complexes

Cited by 68 publications

References 23 publications

Organometallic Polymers with Transition Metals in the Main Chain

Organometallic Polymers with Transition Metals in the Main Chain

Multistate Redox‐Active Metalated Triarylamines

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

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