Absorption and propagation of light in quaterthiophene crystals

We examine absorption of light in quaterthiophene crystals for different directions of the ray and wave-normal vector after refraction on the vacuum/crystal interface. Experimental non-normal incidence spectra are reported where different absorption bands show different behaviour as a function of the angle of incidence. This allows to identify those originating from the b_u Frenkel exciton state.     

Optical absorption spectra of linear and cyclic thiophenes—selection rules manifestation

We theoretically study the size-dependent relation between absorption spectra of thiophene-based oligomers and the corresponding cyclothiophenes. In our approach based on a Frenkel exciton Hamiltonian, we demonstrate that the geometry and selection rules determine the observed relations between the spectra.     

Synthesis and optical properties of tetraphenylmethane-based tetrahedral fluorescent compounds and their water-soluble PEG-linked polymers

The synthesis and optical properties of tetrahedral fluorescent compounds comprising of tetraphenylmethane as the core and oligothiophenes as the chromophoric arms, and their water-soluble poly(ethylene glycol)-linked polymers are reported.     

Thermochromism of bithiophenes and internal aromatic chain rotation

The relation between thermochromism and thermal motion of aromatic rings on model bithiophene and 3-butylbithiophene molecules was studied by molecular dynamics (MD) simulations based on semiempirical AM1 hamiltonian. Theoretical optical spectra at various temperatures are generated from the conformations obtained from MD calculations. Alkyl chains have a tendency to tilt bithiophene fragments from co-planarity (connected with blue shift) whereas the unsubstituted systems prefer the higher degree of planarity (connected with red shift) upon the temperature increase. The slope of the linear temperature dependence of the reciprocal maximal wavelengths consists of the above electronic and of the vibrational contribution that (according to Wien’s displacement law) causes always the increase of the above mentioned slope by reciprocal Wien’s constant. This model explains the temperature dependence of experimental UV–vis spectra for dibutylheptathiophene and 3′,3,4′,4-tetrahexylhexathiophene.     

Oligothienylenevinylenes incorporating 3,4-ethylenedioxythiophene (EDOT) units

A new series of π-conjugated oligomers based on various combinations of thiophene and EDOT units and double bonds has been synthesized by Wittig-Horner reactions from phosphonate anions carrying EDOT or bis-EDOT units. Optical and electrochemical results evidence the crucial role of the EDOT moiety for modulating the electronic properties of the oligomers. The insertion of bis-EDOT unit in the middle of the molecule leads to a self-rigidification of the conjugated system due to non covalent S?O intramolecular interactions. The strong electron donor effect of the EDOT units explains the determining role of the relative position of the EDOT units on the localization and stabilization of the positive charges in the radical cation or dication states.     

Infrared spectra of two sexithiophenes in neutral and doped states: a theoretical and spectroscopic study

The FT-infrared spectra of two sexithiophenes having their end ,′-positions substituted by n-hexyl or -thiohexyl groups, in neutral and doped states, are studied with the main aim of deriving information about the π-electrons delocalization and about the electronic structure of the charged defects created upon doping with iodine. The analysis of the experimental data is aided by Density Functional Theory calculations. The modifications in the electronic structure of the sexithiophene backbone induced by the n-thiohexyl encapsulation are discussed from the point of view of single molecule interactions in thiol-terminated π-conjugated oligomers bound to metallic or cluster electrodes.     

Phosphine Oxide-Functionalized Terthiophene Redox Systems

Main group systems capable of undergoing controlled redox events at extreme potentials are elusive yet highly desirable for a range of organic electronics applications including use as energy storage media. Herein we describe phosphine oxide-functionalized terthiophenes that exhibit two reversible 1e⁻ reductions at potentials below −2 V vs Fc/Fc⁺ (Fc=ferrocene) while retaining high degrees of stability. A phosphine oxide-functionalized terthiophene radical anion was synthesized in which the redox-responsive nature of the platform was established using combined structural, spectroscopic, and computational characterization. Straightforward structural modification led to the identification of a derivative that exhibits exceptional stability during bulk 2 e⁻ galvanostatic charge–discharge cycling and enabled characterization of a 2 e⁻ redox series. A new multi-electron redox system class is hence disclosed that expands the electrochemical cell potential range achievable with main group electrolytes without compromising stability.     

Dielectric tensor and optical spectra of quaterthiophene crystals

We present an approach to the microscopic calculation of the dielectric tensor near the resonances of mechanical Frenkel excitons in a vibronic coupling regime with one effective mode. The model, applied to the prototypical quaterthiophene crystal, is based on a discrete distribution of charges for the evaluation of the molecular transition moment, whilst the coulombic interactions responsible for the exciton delocalization in the crystal are calculated by the Ewald method. From the calculated tensor we simulate absorbance and reflectance spectra and by a direct comparison with the experimental ones, we identify the origin of some shoulders present in the spectra.     

Synthesis and characterization of novel N-carbazole end-capped oligothiophene-fluorenes

A series of novel N-carbazole end-capped oligothiophene-fluorenes was synthesized using Ullmann coupling, bromination, and Suzuki coupling reactions. The optical, thermal, and electrochemical properties of these materials can be tuned by varying the conjugation length of the oligothiophene segment. The terminal carbazole and central fluorene moieties of the resulting materials are beneficial for their morphology, conjugation length, and solubility.     

Non-symmetrical oligothiophenes with ‘incompatible’ substituents

The syntheses of oligothiophenes 1 and 2 comprising two different types of peripheral substituents, namely alkyl and perfluoroalkyl, is reported. The key synthetic step is the Pd-catalyzed cross-coupling of perfluoroalkylated bromide 3 with an appropriate boronate. This molecular design is expected to promote unusual two-layer packing, which is of interest for application in electronic devices. Quaterthiophene 1 forms smectic mesophase, though in the narrow temperature range, and is suitable for the fabrication of thin films by solution processing methods.