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In this study we designed a new class of symmetrical facial oligothiophene amphiphiles, which could be obtained in fewer steps than for previously reported analogues, but still possess the specific substituent sequence to control their backbone curvature. This novel design allows the late-stage introduction of hydrophilic groups, aiding both purification and ease of structure variation. Following the new synthetic scheme, symmetrical ter- and sexi-thiophenes were synthesized, analysed and their properties were compared to their non-symmetrical analogues. Surprisingly, the self-assembly behaviour in water, aggregate morphologies and photo-physical properties turned out to be significantly different despite the same ratio of hydrophilic and hydrophobic substituents. The new substitution pattern resulted in a drastic decrease of the critical aggregation concentration and an increase of the aggregate size. The symmetrical positioning of the substituents also heavily influenced the photo-physical properties. The changes were observed as large blue shifts in the absorption and emission spectra in water when compared to similar regio-regular oligothiophene amphiphiles.

The linear and non-linear optical properties of a family of dumbbell-shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2'-bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non-linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4, with 3 and 6 thiophene rings, respectively), owing to the presence of the (3)π-π* state of the conjugated bridge below the (3)MLCT-emitting states of the end-capping Ru(II) complexes. In contrast, the compound with the shortest bridge (2, one thiophene ring) shows excellent photophysical features. Non-linear optical experiments showed that the investigated compounds were strong non-linear absorbers in wide energy ranges. Indeed, their non-linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two-photon absorption (TPA) but also noteworthy three-photon-absorption behavior, with a cross-section value of 4×10(-78) cm(6) s(2) at 1450 nm. This characteristic was complemented by the strong excited-state absorption (ESA) that was observed for compounds 3 and 4. As a matter of fact, the overlap between the non-linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical-power-limiting applications., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The transformation of bipolarons into polaron pairs in long oligothiophene dications has been reported by Raman spectroscopy. These polaron-pair dicationic species possess singlet open-shell biradicaloid ground electronic states. The formation of biradical polaron pairs marks the end of the quinoidal stability promoted by the intrinsic proaromatic character. The quinoidal stability in TCNQ oligothiophenes in comparison with dicationic oligothiophenes has been addressed.

A comprehensive photophysical and spectroscopic (electronic and Raman) study guided by density functional theory, DFT, CIS, and correlated ab initio calculations has been performed on a series of fully oxidized oligothiophenes with variable chain length, and up to four rings. A comparison with the properties of oligoenes and oligothiophenes is proposed. Absorption, fluorescence, lifetimes, flash-photolysis, phosphorescence, two-photon absorption, Raman, resonance Raman, and thermospectroscopy data are collected and interpreted according to the obtained theoretical results. The interest is focused on the ground electronic state and in the low-lying excited electronic states. Full oxygenation of the sulfur atoms of oligothiophenes results in: (i) restricted inter-ring isomerization such as observed from the absorption spectra; (ii) an effective quenching of fluorescence, and (iii) the appearance of dual emission. The emission features are explained by the interference of a dipole-allowed and a dipole-forbidden singlet excited states leading to simultaneous lighting from a local Frenkel and an intramolecular charge transfer photon-releasing configurations. These two excited states contribute to the broadening of the light emission spectrum. These properties highlight the similarity of these samples to that of oligoenes with comparable number of pi-electrons.

The synthesis and a combined spectroscopic and density functional theoretical characterization of a 3',4'-ethylenedioxy-5,5' '-bis(dicyanomethylene)-5,5' '-dihydro-2,2':5',2' '-terthiophene analogue of 7,7,8,8-tetracyanoquinodimethane (TCNQ) are presented. Electrochemical data show that this novel trimer can be both reversibly reduced and oxidized at relatively low potentials. Quantum-chemical calculations show that the compound exhibits a quinoidal structure in its ground electronic state and that a certain degree of intramolecular charge transfer takes place from the central terthienyl moiety toward both =C(CN)2 end-caps. Therefore, the amphoteric redox behavior of this novel material can be related to the coexistence of an electron-impoverished terthienyl core endowed by two electron-enriched =C(CN)2 substituents. The UV-vis spectrum is dominated by the appearance of a strong absorption near 660 nm, attributable to the highest occupied molecular orbital (HOMO) --> lowest unoccupied molecular orbital (LUMO) pi-pi electronic transition of the terthienyl spine on the basis of time-dependent density functional theory (DFT) computations. The DFT calculations performed on the minimum-energy molecular geometry about the equilibrium atomic charge distribution, topologies, and energies of the frontier orbitals around the gap and about the Raman-active vibrations associated with the strongest Raman features are also consistent with a rather effective pi-electron conjugation and the partial degree of intramolecular charge transfer mentioned above. Our study reveals this novel heteroquinoid trimer could act as a promising candidate in organic field-effect transistor (OFET) applications.

This paper presents a combined experimental Raman and density functional theory (DFT) study of a series of oligothiophenes with variable pi-core lengths and substituted at the alpha,omega- and beta,beta'-terminal positions with perfluorohexyl, perfluorohexylcarbonyl, perfluoroarene, and cyano groups. The study covers the neutral and the electrochemically oxidized samples. The spectra have been assigned with the help of B3LYP/6-31G** calculations and interpreted by the predictions of effective conjugation coordinate (ECC) theory. Direct relationships between the bond length alternation (BLA) parameters and the Raman wavenumbers of the two most important bands of the spectra have been outlined showing the collective character of their electronic and vibrational properties. It is found that the topology of the thienyl electronic structure is not uniform along the conjugated core with the external rings more aromatic, whereas for the innermost part the pi-electron delocalization is greater and extends with the increment of chain length. Perfluorohexyl substitution finely tunes the electronic properties via negative inductive effects. The beta,beta' isomers exhibit larger conformational distortion, which strongly modifies the mean conjugation length. Oxidation provokes electronic structure quinoidization spreading over the whole system but more marked in the central part of the pi-core. The Raman features associated to quinoidization in the oxidized species have been interpreted in relation to the oligomer core length and the substitution regiochemistry.

A series of radial thiophene-based structures consisting of a central benzene or thiophene ring surrounded by acetylene-bridged terthienyl arms has been investigated by physical and theoretical methods. Fourier transform Raman spectroscopy of the neutral solids shows that the terthiophene arms are weakly coupled across the core (benzene plus acetylene groups) likely due to cross-conjugation or meta-conjugation effects that may prevent full delocalization. By increasing the number of arms around the central ring, the electronic structure of the molecules seems to be affected only at the core, whereas the outer terthiophene arms remain almost unaltered. Raman spectroelectrochemistry and quantum chemical calculations provide further insight into the charge delocalization of the oxidized species. There is no evidence to suggest that these oxidized forms, obtained upon electrochemical doping of the molecules, show charge delocalization across the core., ((c) 2004 American Institute of Physics.)

The UV/Vis, infrared absorption, and Raman scattering spectra of 3',4'-dibutyl-5,5"-bis(dicyanomethylene)-5,5"-dihydro-2,2':5',2"-terthiophene have been analyzed with the aid of density functional theory calculations. The compound exhibits a quinoid structure in its ground electronic state and presents an intramolecular charge transfer from the terthiophene moiety to the C(CN)2 groups. The molecular system therefore consists of an electron-deficient terthiophene backbone end-capped with electron-rich C(CN)2 groups. The molecule is characterized by a strong absorption in the red, due to the HOMO-->LUMO pi-pi* electronic transition of the terthiophene backbone that shifts hypsochromically on passing from the solid state to solution and with the polarity of the solvent. The analysis of the vibrational spectra confirms the structural conclusions and supports the existence of an intramolecular charge transfer. Vibrational spectra in several solvents and as a function of temperature have also been studied. Significant frequency upshifts of the vibrations involved in the pi-electron-conjugated pathway have been noticed upon solution in polar solvents and with the lowering of the temperature. Finally, we propose a quinoid molecule as a reliable structural and electronic model for dication species in doped oligothiophenes or for bipolaron charged defects in doped polythiophene.

A combination of Raman spectroscopy and density functional theory calculations is used to describe the structural and spectroscopic properties of the different isomeric cations of diferrocenyl quaterthiophenes. Isomerisation of the thienyl β-positions provides site selective oxidation, which gives rise to species that can interconvert by moving the charge over the bridge. The spectroscopic study allows us to describe a sequence of stationary trapped cationic, either ferrocenyl or thienyl, states which constitutes an energy cascade of accessible sites through which the charge transfer can proceed. [ABSTRACT FROM AUTHOR]

This paper reports on a combined spectroscopic and density functional theory study on a series of cyclo(diacetylenes-oligothiophenes) with different shapes and dimensions. The case of a macrocycle fragmented by the insertion of Pt metallic atoms is illustrated as well. The analysis covers the neutral and oxidized samples. A full assignment of the spectra has been proposed, supported by BP86/cc-pVDZ theoretical calculations. Ring shape and molecular dimension have been related with the C==C/C–C structural parameters and Raman wave numbers. Platinum atom insertion within the acetylene spacer seems to soften ring strain owing to the rupture of the strained circular shape. Oxidation causes an overall downshift of the Raman wave numbers likely due to the skeletal relaxation of CC conjugated path, while the ring shape of each macrocycle is conserved upon oxidation. [ABSTRACT FROM AUTHOR]

This article investigates the excited and charged states of three branched oligothiophenes with methyl-thienyl side groups as models to promote 3D arrangements. A comparison with the properties of the parent systems, linear all-α,α-oligothiophenes, is proposed. A wide variety of spectroscopic methods (i.e., absorption, emission, triplet-triplet transient absorption, and spectroelectrochemistry) in combination with DFT calculations have been used for this purpose. Whereas the absorption spectra are slightly blueshifted upon branching, both the emission spectra and triplet-triplet absorption spectra are moderately redshifted; this indicates a larger contribution of the β-linked thienyl groups in the delocalization of the S1 and T1 states rather than into the S0 state. The delocalization through the α,β-conjugated path was found to be crucial for the stabilization of the trication species in the larger branched systems, whereas the linear sexithiophene homologue can only be stabilized up to the dication species. [ABSTRACT FROM AUTHOR]

A series of push-pull chromophores built around thiophene-based π-conjugating spacers and bearing various types of amino-donors and cyanovinyl-acceptors have been analyzed by means of UV-Vis-NIR spectroscopic measurements. Density functional theory (DFT) calculations have also been performed to help the assignment of the most relevant electronic features and to derive useful information about the molecular structure of these NLO-phores. The effects of the donor/acceptor substitution in the electronic and molecular properties of the π -conjugated spacer have been addressed. The effectiveness of the intramolecular charge transfer (ICT) has also been tested as a function of the nature of the end groups (i.e., electron-donating or electron-withdrawing capabilities). [ABSTRACT FROM AUTHOR]

In the present paper, the synthesis and characterization of 2,2′-bis{bi[2,2’-(3,4-ethylenedioxy)thiophen-5-yl]}-3,3′-bithianaphthene, nicknamed BT 2 E 4 , is reported. We show that electrooligomerization of BT 2 E 4 leads to electroactive films which are evaluated by cyclic voltammetry (CV), UV/vis spectroelectrochemistry and CV coupled with in-situ conductance measurements. Direct comparisons to the properties of the oligomers obtained from the atropisomeric all-thiophene analogue BT 2 T 4 show that the introduction of EDOT leads to a strong reduction of the band-gap, an overall red-shifted absorption spectrum and a rigidification of the structure. Finally, DFT and TD-DFT calculations were performed in parallel to investigate and to compare the electronic and molecular structures of neutral and charged monomer and oligomer species. [ABSTRACT FROM AUTHOR]

Abstract: The Raman spectra of a vinylene-bridged quaterthiophene with their thienyl β-positions occupied by hexyl groups and with the terminal α,α′ sites substituted with ferrocene and dicyano-vinylene groups in symmetric and asymmetric fashions have been reported on. The Raman lines have been assigned to vibrational normal modes with the help of theoretical calculations in the framework of the density functional theory. There is spectroscopic evidence that substitution with two ferrocene groups leads to a central conjugated backbone with increased conjugation. Donor/acceptor substitution however provokes the appearance of a molecular subunit around the ferrocene group characterized by the aromatic character of the thiophene rings, while in the proximity of the dicyano-vinyl group the thienyl rings acquire a pseudo-quinoidal structure. [Copyright &y& Elsevier]