Toward the Development of Molecular Wires:  A Terpyridine Spacer Containing Polyferrocenylalkyne Linkages

Abstract

The preparation, characterizations, and electrochemical measurements of the terpyridine-ferrocenylalkyne spacers (tpy−C⋮C−(fc) n −C⋮C−tpy; tpy = terpyridyl; fc = ferrocenyl; n = 2, 3) are described. In the electrochemical measurements, the charge could be delocalized to the cyclopentadienyl and ethynyl moieties caused by the built-up charge density upon oxidation of the ferrocenyl moiety.

1,1′‐Diaryl‐Substituted Ferrocenes: Up to Three Hinges in Oligophenyleneethynylene‐Type Molecular Wires

“…Other [31] 1,1Ј-dicyanoferrocene, [32] and a triferrocenyldialkyne. [33] The importance of the eclipsed conformations of 1,1Ј-disubstituted ferrocenes is, however, documented by the facile formation of [4]ferrocenophanes from 1,1Ј-dialkynylferrocenes. [21,23,24] Another remarkable feature of the structure is the almost perfect coplanarity of the cyclopentadienyl and thiophene rings with a deviation from coplanarity of only 5-7°, which indicates that the conjugation will not be interrupted by a significant torsion between the thiophenylene and ferrocene substructures.…”

Long-distance electronic interaction in a molecular wire consisting of a ferrocenyl–ethynyl unit bridging two [(η5-C5H5)(dppe)M] metal centers

“…Samples of 1 and (g 5 -C 5 H 5 )(dppe)MCl were prepared according to the literature procedure [44][45][46]. Preparations of the ferrocenyl-ethynyl spacers (8-10) were described in our previous paper [26][27][28]. As shown in Schemes 1 and 2, complexes of 1-7 could be prepared.…”

“…A mixture of 11 (50 mg, 0.12 mmol) [27], (g 5 -C 5 H 5 )(dppe)FeCl (200 mg, 0.36 mmol) [46], KPF 6 (130 mg, 0.72 mmol) was stirred in methanol (30 ml) at room temperature. After stirring for 2 h, potassium tert-butoxide (56 mg, 0.5 mmol) was added to the solution.…”

“…doi:10.1016/j.jorganchem.2008. 12.056 bis-(2,2 0 :6 0 ,2 00 -terpyridyl)polyferrocene redox-active spacers endcapped with photoactive and redox-active Ru 2+ -terpyridine terminals ([(tpy)Ru II -(tpy-(fc) n -tpy)-Ru II (tpy)] 4+ (tpy = terpyridine, fc = ferrocenyl, n = 1-3) and [(tpy)Ru II -(tpy-C"C-(fc) n -C"C-tpy)-Ru II (tpy)] 4+ (n = 2-3)) to study the electronic interaction between the end-capped Ru 2+ metal centers [26][27][28]. In our previous papers, the CV electrochemical measurements for these binuclear Ru 2+ complexes were dominated by the Ru 2+ /Ru 3+ redox couple (E 1/2 from 1.35 to 1.38 V), Fe 2+ /Fe 3+ redox couples (E 1/2 from 0.4 to 1.0 V) and tpy/tpy À /tpy 2À redox couples (E 1/2 from À1.3 to À1.5 V).…”

p‐Phenyleneethynylene Molecular Wires: Influence of Structure on Photoinduced Electron‐Transfer Properties

“…[5] In this context, intramolecular electron transfer along conjugated chains of oPPV has been tested in several donor-acceptor conjugates involving anilines, [6] porphyrins [7] or ferrocenes [8] as electron donors on one side, and [60]fullerenes, on the other side, as the electron acceptor. [9] In fact, in a pioneering study tetracene (TET; as electron donor) and pyromellitimide (PYR; as electron acceptor) were connected by means of oPPV of increasing length (TET-oPPV-PYR).…”