The full UV-visible dielectric tensor and the corresponding directions of the principal axes of triclinic tetracene crystals are reported as deduced either by polarized absorption and ellipsometry measurements or by calculations based on the molecular and crystallographic data. The results allow the attribution of the polarized bands observed in both absorption and photoluminescence emission spectra. In particular, the spectral line shape and polarization of the emission are found to depend on the sample thickness, and the effect is attributed to the modification of the state of polarization of the emitted light during its propagation inside the crystal. Indeed, the directions of polarization of the lowest optical transitions and the directions of the principal axes of the dielectric tensor are demonstrated not to coincide, in contrast to the assumptions typically made in the literature, thus causing the mixed transverse/longitudinal character of light propagation.

A major challenge in molecular electronics is to develop logic devices based on a truly intramolecular switching mechanism. Recently, a new type of molecular device has been proposed where the switching characteristic is mediated by the bistability in the position of the two hydrogen atoms which can occupy different, energetically equivalent positions (tautomerization) in the inner cavity of porphyrins and naphthalocyanines. Up to now, such a reaction has only been exploited at low temperatures and induced or detected through atomic scale manipulation. In addition, the unpredictability of the tautomer orientation currently excludes molecular interconnection to functional electronic circuits. Here, full evidence is provided that, following a newly proposed growth strategy, 2D layers of metal-free tetraphenylporphyrins (H2TPP) show frozen tautomerization even at room temperature on macroscopic domains, with the H atoms aligned along a direction settled a priori. This behavior is ascribed to the buckling of the molecule, anchored to the substrate, which removes the degeneracy between the two tautomer alignments. On this basis, a new way to exploit uniaxially oriented H2TPP tautomers in a first elementary logic device is proposed

Exciton-phonon (EP) coupling in molecular aggregates is reexamined in cases where extended intermolecular interactions result in low-energy excitons with high effective masses. The analysis is based on a single intramolecular vibrational mode with frequency omega0 and Huang-Rhys factor lambda2. When the curvature Jc at the exciton band bottom is much smaller than the free-exciton Davydov splitting W, the strength of the EP coupling is determined by comparing the nuclear relaxation energy lambda2omega0 with the curvature. In this way, weak (lambda2omega0<<4piJc), intermediate I (lambda2omega0 approximately 4piJc), and strong I (lambda2omega0>>4piJc) coupling regimes are introduced. The conventional intermediate (lambda2omega0 approximately W) and strong (lambda2omega0>>W) EP coupling regimes originally defined by Simpson and Peterson [J. Chem. Phys. 26, 588 (1957)] are based solely on the Davydov splitting and are referred to here as intermediate II and strong II regimes, respectively. Within the intermediate I and strong I regimes the near degeneracy of the low-energy excitons allows efficient nonadiabatic coupling, resulting in a spectral splitting between the b- and ac-polarized first replicas in the vibronic progression characterizing optical absorption. Such spectral signatures are clearly observed in OT4 thin films and crystals, where splittings for the lowest energy mode with omega0=161 cm(-1) are as large as 30 cm(-1) with a small variation due to sample disorder. Numerical calculations using a multiphonon BO basis set and a Hamiltonian including linear EP coupling yield excellent agreement with experiment.

Organic-organic epitaxy is a successful strategy for growing highly oriented and crystalline heterojunctions of organic semiconductors. Within this class of materials, crystalline rubrene is especially promising because of its outstanding hole mobility. Here, the (200) surface of rubrene single crystals was used as substrate for growing thin films of another organic semiconductor: R-quaterthiophene. The film growth proceeds via a 3D mechanism, with the formation of a fewmonolayer-thick crystalline islands oriented along two main directions, as deduced by the optical reflection of the R-quaterthiophene/rubrene heterostructure measured over macroscopic regions. An atomic-scale analysis of the film surface performed with scanning force microscopy revealed a complete textural order achieved through a line-on-line epitaxial relation. With the help of empirical force-field calculations of the heteroepitaxial interface, this orienting propensity is demonstrated to be strictly related to the peculiar corrugation of the rubrene crystal surface, showing marked furrows along two orthogonal crystallographic directions.