Probing excited state electronic communications across diethynyl-[2.2]paracyclophane-containing conjugated organometallic polymers

Clément, Sébastien; Goudreault, Thomas; Bellows, Diana; Fortin, Daniel; Guyard, Laurent; Knorr, Michael; Harvey, Pierre D.

doi:10.1039/c2cc34163h

Cited by 26 publications

(13 citation statements)

References 26 publications

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“…Very recently, Knorr, Harvey, and co-workers reported the triplet k ET value for energy transfer through [2.2]paracyclophane in a platinum-containing through-space conjugated polymer. The k ET value by the Dexter mechanism was estimated to be approximately on the order of 10 5 s À1 , 12 which is much smaller than the k ET value for transfer by the Fçrster mechanism discussed above. [22] Thus, it is concluded that in our system, the Fçrster-type energy transfer is dominant because of the fixation of the donor and acceptor in close proximity (small R value), the good spectral overlap between the PL spectrum of the donor and the absorption spectrum of the acceptor (large J value), and the favorable orientation of the donor and acceptor (large k 2 value).…”

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confidence: 75%

“…However, conjugated polymers containing cyclophane skeletons in the conjugated polymer main chain have been ignored until recently. [5,[9][10][11][12] We have incorporated [2.2]paracyclophane into conjugated polymer backbones and evaluated the various characteristics of cyclophane-based through-space conjugation. To obtain a better understanding of these through-space conjugated polymers, herein, we prepared a through-space conjugated dimer, in which two pelectron systems are stacked in a single molecule.…”

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confidence: 99%

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Energy‐Transfer Properties of a [2.2]Paracyclophane‐Based Through‐Space Dimer

Morisaki

Kawakami

Nakano

et al. 2013

Chemistry A European J

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confidence: 75%

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confidence: 99%

Energy‐Transfer Properties of a [2.2]Paracyclophane‐Based Through‐Space Dimer

Morisaki

Kawakami

Nakano

et al. 2013

Chemistry A European J

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“…Absorption (abs), excitation (grey), and emission spectra of HC CÀPCPÀC CH (55; in 2MeTHF, 77 K; up) (Àtrans-Pt(PBu 3 ) 2 ÀC CÀPCPÀC CÀ) n (56; in 2MeTHF, 77 K; middle) and (ÀPt 2 (dppm) 2 ÀC CÀPCPÀC CÀ) n (57; solid state, 298 K; bottom). [72] Figure 25.…”

Section: [22]paracyclophane-containing Polymersmentioning

confidence: 96%

“…Stuctures of the bis(ethynyl)[2.2]paracyclophane-containing polymers. [72] Co 2 (CO) 6 (m-h 2 -PCPÀC CH) [69] (51) for which the coloured Co 2 (CO) 6 cluster unit exhibits non-luminescent lower energy S 1 and T 1 excited states ( Figure 23). These investigations are clearly important in order to address the behaviour in conjugated organometallic polymers built upon bis(ethynyl)ÀPCP bridges.…”

Section: [22]paracyclophane-containing Polymersmentioning

confidence: 99%

Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans‐Bis(para‐ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives

Wong

Harvey

2010

Macromol. Rapid Commun.

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186

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This review article surveys the electronic and photophysical properties of conjugated organometallic polymers built upon the title compound and its related derivatives focussing primarily on systems investigated in our laboratories. The general structure of the polymers is (trans-bis(para-ethynylbenzene)bis(phosphine)platinum(II)-G)(n) where G is a conjugated group such as thiophene, fluorene, carbazole, substituted silole, quinone derivative, and metalloporphyrin residue, or a non-conjugated main-group moiety. Systems based on substituted phenylene units and other related fused rings are also discussed. The phosphine ligands are generally triethyl- or tri-n-butylphosphine groups. These trans-platinum(II) polymers and the corresponding model compounds are compared to the corresponding ortho-derivatives in the quinone series, and the newly prepared paracyclophane-containing polymers. For the porphyrin series, a comparison of fully conjugated oligomers exhibiting the general structure (trans-bis(para-ethynyl(zinc(porphyrin)))bis(phosphine)platinum(II))(n) (i.e., the C(6) H(4) group is absent from the main chain) will be made. This contribution also includes a description of the properties of the mononuclear chromophore itself, properties that define those of the polymers. Potential applications with regard to electronic and optical devices will be highlighted. These soluble and stable materials feature both the processing advantages of polymers and the functionality provided by the presence of metal centers. These multifunctional organometallic polyyne polymers exhibit convenient structural variability as well as optical and electronic properties, which renders them important for use in different research domains as chemical sensors and sensor protectors, as converters for light/electricity signals, and as patternable precursors to magnetic metal alloy nanoparticles.

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“…The theoretical calculations described above were carried out on the assumption that Förster‐type7 energy transfer occurred, disregarding the Dexter‐type11 energy transfer. Recently, Knorr and Harvey reported the triplet‐state energy transfer, which is performed by the Dexter mechanism, using platinum‐containing through‐space conjugated copolymers 12. The k ET values were calculated to be on the order of 10 4 –10 5 s −1 .…”

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confidence: 99%

Through‐Space Conjugated Molecular Wire Comprising Three π‐Electron Systems

Morisaki¹,

Kawakami²,

Shibata³

et al. 2014

Chemistry An Asian Journal

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A [2.2]paracyclophane-based through-space conjugated oligomer comprising three π-electron systems was designed and synthesized. The arrangement of three π-conjugated systems in an appropriate order according to the energy band gap resulted in efficient unidirectional photoexcited energy transfer by the Förster mechanism. The energy transfer efficiency and rate constants were estimated to be >0.999 and >10(12) s(-1), respectively. The key point for the efficient energy transfer is the orientation of the transition dipole moments. The time-dependent density functional theory (TD-DFT) studies revealed the transition dipole moments of each stacked π-electron system; each dipole moment was located on the long axis of each stacked π-electron system. This alignment of the dipole moments is favorable for fluorescence resonance energy transfer (FRET).

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Probing excited state electronic communications across diethynyl-[2.2]paracyclophane-containing conjugated organometallic polymers

Abstract: The triplet k(ET) for three organometallic polymers built upon the diethynyl[2.2]paracyclophane was studied to show good excited state electronic communication across the materials.

Cited by 26 publications

References 26 publications

Energy‐Transfer Properties of a [2.2]Paracyclophane‐Based Through‐Space Dimer

Energy‐Transfer Properties of a [2.2]Paracyclophane‐Based Through‐Space Dimer

Recent Progress on the Photonic Properties of Conjugated Organometallic Polymers Built Upon the trans‐Bis(para‐ethynylbenzene)bis(phosphine)platinum(II) Chromophore and Related Derivatives

Through‐Space Conjugated Molecular Wire Comprising Three π‐Electron Systems

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