Photoinduced charge transport over branched conjugation pathways: donor–acceptor substituted 1,1-diphenylethene and 2,3-diphenylbutadiene

Walree, Cornelis A. van; Wiel, Bas C. van der; Williams, René M.

doi:10.1039/c3cp52148f

Cited by 10 publications

(8 citation statements)

References 61 publications

(96 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Especially in D–A conjugated polymers the influence of cross-conjugation is expected to be significant as it might (partially) block electronic communication between electron-rich and -poor parts. Although hampered, weak electronic communication through cross-conjugated bonds has been shown in donor–acceptor substituted small molecules with a different number of cross-conjugated linkages. − The influence of cross-conjugation has, to the best of our knowledge, never been investigated systematically in the important class of materials formed by donor–acceptor conjugated copolymers.…”

Section: Introductionmentioning

confidence: 99%

Effects of Cross-Conjugation on the Optical Absorption and Frontier Orbital Levels of Donor–Acceptor Polymers

et al. 2015

View full text Add to dashboard Cite

The influence of cross-conjugation on the optical and electrochemical properties of donor−acceptor copolymers is investigated. Isoindigo, substituted at the 6,6′ or the 5,5′ positions, and thieno[3,2-b]thiophene and thieno [2,3-b]thiophene are taken as conjugated and cross-conjugated electron-deficient and electron-rich building blocks from which four isomeric donor−acceptor polymers were synthesized. Introducing cross-conjugation in isoindigo has only a small effect on the electrochemical band gap and on the onset of the absorption, which remains in the near-infrared. The optical absorption spectra, however, differ strongly because crossconjugation strongly reduces the absorption coefficient. DFT calculations confirm that the transition to the lowest excited singlet state has a small oscillator strength in cross-conjugated isoindigo model compounds. Cross-conjugation in thienothiophene exerts a different effect. It causes a moderate but distinct blue-shift of the optical absorption and a deeper HOMO energy level.

show abstract

Section: Introductionmentioning

confidence: 99%

Effects of Cross-Conjugation on the Optical Absorption and Frontier Orbital Levels of Donor–Acceptor Polymers

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Depending on the donor and acceptor, either the TICT emission or the normal emission competes with the photoisomerization in other donor-acceptor substituted stilbenes. 18,19,21,[29][30][31][32] It is reported that torsional modes of both energy surfaces are decoupled with the PICT state as a precursor in trans-aminostilbenes. Apart from stilbene analogues, photoinduced ICT emission is also reported in other higher polyenes, including push-pull dyes and donor-acceptor substituted non-styryl olefins.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced intramolecular charge transfer in trans-2-[4′-(N, N-dimethylamino)styryl]imidazo[4,5- b]pyridine: effect of introducing a C=C double bond

Mishra

Sahu

Tripathi

et al. 2014

Photochem Photobiol Sci

View full text Add to dashboard Cite

The spectral characteristics of trans-2-[4'-(N,N-dimethylamino)styryl]imidazo[4,5-b]pyridine (t-DMASIP-b) have been investigated using absorption and fluorescence techniques, and compared with 2-(4'-N,N-dimethylamino)imidazo[4,5-b]pyridine (DMAPIP-b). The study reveals that introduction of a C[double bond, length as m-dash]C double bond strongly perturbs the photophysics of the system. Unlike DMAPIP-b, t-DMASIP-b emits a single emission in aprotic and protic solvents. The emission occurs from the locally excited state in nonpolar solvents and from a planar intramolecular charge transfer (PICT) state in polar solvents. Multiple linear regression analysis suggests that among the different solvent parameters, the dipolar interaction contributes more to the stabilization of the system in both the ground and excited states. Theoretical calculations suggest that, unlike in DMAPIP-b, proton coupled twisted intramolecular charge transfer (TICT) emission does not occur in t-DMASIP-b. The higher quantum yield obtained in the viscous solvent glycerol is attributed to the restriction of the twisting of the olefinic bond. The photoirradiation of t-DMASIP-b shows that isomerization takes place in all solvents, including viscous glycerol. The theoretically simulated potential energy surface shows that isomerization occurs via a phantom state, which is a nonradiative process. The rise in temperature favors the photoisomerization, thus, the fluorescence quantum yield decreases. The prototropic study indicates that, unlike in DMAPIP-b, the protonation takes place at different places to form the monocations.

show abstract

“…[8] Cross-conjugated molecules are well known, [9] and some representative examples are shown in the upper panel of Figure 1, including 1,1-diethynylalkene (A), [10] [3]dendralene (B), [11] and 1,1-diphenylalkene (C). [12] These components have been widely used in the design of molecular materials with optoelectronic functions.…”

Section: Introductionmentioning

confidence: 99%

Conformation‐Determined Through‐Bond versus Through‐Space Electronic Communication in Mixed‐Valence Systems with a Cross‐Conjugated Urea Bridge

Gong

Zhong

Yao

2014

Chemistry A European J

View full text Add to dashboard Cite

Bis-triarylamine 2 and cyclometalated diruthenium 6(PF6)2 with a linear trans,trans-urea bridge have been prepared, together with the bis-triarylamine 3 and cyclometalated diruthenium 8(PF6)2 with a folded cis,cis-N,N-dimethylurea bridge. The linear or folded conformations of these molecules are supported by single-crystal X-ray structures of 2, 3, and other related compounds. These compounds display two consecutive anodic redox waves (N(·+/0) or Ru(III/II) processes) with a potential separation of 110-170 mV. This suggests that an efficient electronic coupling is present between two redox termini through the cross-conjugated urea bridge. The degree of electronic coupling has been investigated by using spectroelectrochemical measurements. Distinct intervalence charge-transfer (IVCT) transitions have been observed for mixed-valent (MV) compounds with a linear conformation. The IVCT transitions can also be identified for the folded MV compounds, albeit with a much weaker intensity. DFT results support that the electronic communication occurs by a through-bond and through-space pathway for the linear and folded compounds, respectively. The IVCT transitions of the MV compounds have been reproduced by TDDFT calculations. For the purpose of comparison, a bistriarylamine and a diruthenium complex with an imidazolidin-2-one bridge and a urea-containing mono-triarylamine and monoruthenium complex have been synthesized and studied.

show abstract

Photoinduced charge transport over branched conjugation pathways: donor–acceptor substituted 1,1-diphenylethene and 2,3-diphenylbutadiene

Cited by 10 publications

References 61 publications

Effects of Cross-Conjugation on the Optical Absorption and Frontier Orbital Levels of Donor–Acceptor Polymers

Effects of Cross-Conjugation on the Optical Absorption and Frontier Orbital Levels of Donor–Acceptor Polymers

Photoinduced intramolecular charge transfer in trans-2-[4′-(N, N-dimethylamino)styryl]imidazo[4,5- b]pyridine: effect of introducing a C=C double bond

Conformation‐Determined Through‐Bond versus Through‐Space Electronic Communication in Mixed‐Valence Systems with a Cross‐Conjugated Urea Bridge

Contact Info

Product

Resources

About