Silvia Destri

Thiophene Based Europium β-Diketonate Complexes: Effect of the Ligand Structure on the Emission Quantum Yield

The synthesis and the molecular and photophysical characterization, together with solid state and solution structure analysis, of a series of europium complexes based on β-diketonate ligands are reported. The Eu(III) complex emission, specifically its photoluminescence quantum yield (PL-QY), can be tuned by changing ligands which finely modifies the environment of the metal ion. Steady-state and time-resolved emission spectroscopy and overall PL-QY measurements are reported and related to geometrical features observed in crystal structures of some selected compounds. Moreover, paramagnetic NMR, based on the analogous complexes with other lanthanides, are use to demonstrate that there is a significant structural reorganization upon dissolution, which justifies the observed differences in the emission properties between solid and solution states. The energy of the triplet levels of the ligands and the occurrence of nonradiative deactivation processes clearly account for the luminescence efficiencies of the complexes in the series.

Electroluminescent poly(fluorene-co-thiophene-S,S-dioxide): synthesis, characterisation and structure–property relationships

A new copolymer, constituted by the regular alternation of a fluorene derivative with a 1,1-dioxothiophene moiety, has been synthesised via Suzuki coupling. The molecular, thermal, structural, and photophysical characterisations have been performed. The material showed two dimensional order, enhanced by annealing; molecular modelling calculations afforded a consistent structural model accounting for the optical data. In comparison with both polyfluorenes and 1,1-dioxothiophene oligomers the unusual photoluminescence quantum yields observed in solution and in the solid state can be related to a significant contribution of internal conversion to the deactivation process in solution, and the formation of intra-chain hydrogen-bonds, due to a peculiar chain conformation, in the solid state. LED devices based on this new copolymer showed the highest efficiency compared with similar copolymers containing both fluorene and 1,1-dioxothiophene functionalities.

Near‐IR Emitting Iridium(III) Complexes with Heteroaromatic β‐Diketonate Ancillary Ligands for Efficient Solution‐Processed OLEDs: Structure–Property Correlations

Three NIR-emitting neutral Ir(III) complexes [Ir(iqbt)2 (dpm)] (1), [Ir(iqbt)2 (tta)] (2), and [Ir(iqbt)2 (dtdk)] (3) based on the 1-(benzo[b]thiophen-2-yl)-isoquinolinate (iqtb) were synthesized and characterized (dpm=2,2,6,6-tetramethyl-3,5-heptanedionate; tta=2-thienoyltrifluoroacetonate; dtdk=1,3-di(thiophen-2-yl)propane-1,3-dionate). The compounds emit between λ=680 and 850 nm with high luminescence quantum yields (up to 16 %). By combining electrochemistry, photophysical measurements, and computational modelling, the relationship between the structure, energy levels, and properties were investigated. NIR-emitting, solution-processed phosphorescent organic light-emitting devices (PHOLEDs) were fabricated using the complexes. The devices show remarkable external quantum efficiencies (above 3 % with 1) with negligible efficiency roll-off values, exceeding the highest reported values for solution-processible NIR emitters.

A new apparatus for ultra-high vacuum organic molecular beam deposition

The conceptual and technical description of a multi-chamber apparatus for the ultra high vacuum fabrication of highly ordered organic superstructures, recently designed and assembled in our group, is reported. Both the basic criteria for the project and the technical choices made are illustrated for all the instruments installed in the different chambers, with particular emphasis on the effusion cells and on the in situ characterization facilities.

Optical Properties and Photoexcitations in Regularly Alternating Conjugated Copolymers

We report in this short paper a preliminary account on the design, preparation, optical characterization and photoexcitation of a class of novel conjugated polymers consisting of regularly alternating thiophene and benzene sequences, which Might represent Models for one-dimensional superlattices. Optical absorption and emission spectra suggest that the barriers produced by the phenylene Moieties do not interrupt the conjugation but can produce localization effects. Resonant Raman spectra indicate that a selective response of the thiophene Moiety occurs upon excitation with visible light. Moreover these Measurements confirm the presence of a confinement on the thiophene blocks, while the biphenil Moiety does not appear to feel the energy barrier and behaves as the corresponding polymer poly (paraphenylene) (PPP). CW photomodulation spectra show that the formation of long-lived bipolarons takes place only if the thienylenic Moiety is long enough to accomodate the lattice distortion.

Synthesis and crystal structure and optical properties of fluorenic-core oligomers

Fluorenic core oligomers, displaying interesting photoluminescence properties, have been synthesized by an organometallic route. The crystal and molecular structure of a fluorene derivative and three homologous oligomers have been studied. The spiro-derivative of dibromofluorene shows a very strong interaction between the H and Br atoms. The thienyl-terminated oligomer with a spiro-substituent adopts a particular herringbone arrangement with overlap of only the end-thienyl residues, conformationally disordered. The crystal of the all-phenyl derivative consists of the packing of discrete molecules cofacially arranged. The molecule with linear alkyl chains on the 9-position of the fluorene core and thienyl rings as end-groups exhibits polymorphism and its crystal structure, tetragonal, is very peculiar because of the loose packing allowing a good separation among adjacent thienyl rings. The absorption and emission properties of this series were investigated and the electroluminescence of single-layer devices was characterized. The photoluminescence properties of the molecules are strongly dependent on their structural organization, displaying a red-shift of the emission from the amorphous phase, to the crystalline structure, to the aggregated form. A comparison of the packing of these oligomers and oligothienylenes fully accounts for the optical properties of the reported molecules.

Synthesis and characterization of new azomethine derivatives exhibiting liquid crystalline properties

Azomethine liquid crystals (LCs), constituted by symmetric and asymmetric bithiophene or fluorene units as chromophores, were designed and synthesised. Their thermotropic behaviour was investigated using optical microscopy, differential scanning calorimetry, and wide angle X‐ray diffraction. A lowering of transition temperatures was obtained by the introduction of the lateral methyl group as compared with unsubstituted compounds. The observed LC phases possess the classical textures of calamitic LCs. The optical properties of the target compounds were evaluated, both in solution and in solid state. A blue fluorescence was observed for fluorene containing compounds and a green fluorescence was observed for analogous bithiophene containing compounds. The introduction of a methyl lateral group onto the aromatic rings led to a remarkable increase in the solution emission properties.

Non‐Resonant z‐Scan Characterization of the Third‐Order Nonlinear Optical Properties of Conjugated Poly(thiophene azines)

The nonlinear optical properties of a functionalized poly(thiophene azine), namely, poly(3,4-didodecylthiophene azine), PAZ, at the optical telecommunication wavelength of 1550 nm are investigated by means of the closed-aperture z-scan technique in both thin films and solutions. Values of chi((3))=(2.4+/-0.4)x10(-13) esu, n(2)=(4.0+/-0.7)x10(-15) cm(2) W(-1), and gamma=(4.5+/-0.7)x10(-34) esu are estimated for the third-order (Kerr) susceptibility, the intensity-dependent refractive index, and the molecular second hyperpolarizability of solution samples, respectively. A very small dependence on the polymer chain length is found. Markedly higher values of (4.4+/-1.1)x10(-11) esu, (6.6+/-1.0)x10(-13) cm(2) W(-1), and (5.0+/-0.8)x10(-33) esu are measured for the corresponding quantities in thick (up to 20 mum) polymer films cast on quartz plates. The enhancement of the NLO responses on going from solution to solid samples is attributed to a partially ordered structure and to the presence of interchain interactions leading to greater pi-electron delocalization in the cast polymer films. The results are compared with those previously obtained by using third-harmonic generation (THG), taking into account that those data were measured under conditions of three-photon resonance, whereas our z-scan measurements are fully off-resonance.

Bridging the gap – structure determination of the red polymorph of tetrahexylsexithiophene by Monte Carlo simulated annealing, first-principles DFT calculations and Rietveld refinement

The crystal structure of the red polymorph of tetrahexylsexithiophene (THST) is solved from X-ray powder diffraction data by a direct-space Monte Carlo simulated-annealing approach. First-principles density functional theory (DFT) calculations are used to distinguish between three nearly identical solutions in the space groups C2/m, C2 and P\bar{1} and to improve the overall accuracy of the crystal structure. The correct space group is found to be C2/m. In all space groups, the thiophene backbone is planar and the hexyl side chains assume an all-trans conformation except for two terminal methyl residues, which adopt a gauche orientation. The ability of first-principles DFT calculations to provide atomic coordinates of single-crystal quality is demonstrated by lattice-energy minimization of the known crystal structure of the yellow polymorph of THST. The combination of Monte Carlo simulated annealing, first-principles DFT calculations and Rietveld refinement presented in this paper is generally applicable. It provides a powerful alternative to standard approaches in cases where the information content of the powder diffraction pattern alone is insufficient to distinguish between different structure solutions. DFT calculations can also provide invaluable guidance in Rietveld refinement.

Design preparation and properties of regularly alternating conjugated low molecular weight copolymers based on thienylene-azomethine moietics

A series of low molecular weight copolymers, composed of a sequence of thienylenic (low energy gap) and phenylenic (high energy gap) residues linked together by azomethinic moieties, was prepared and extensively characterized. The semicrystalline materials, showing a weight loss of about 20% up to 450 °C, are soluble in H2SO4 and, when complexed with GaCl3, in CH3NO2. The molecular structure was derived from FT-IR, viscosity, 1H NMR and electron spin resonance analyses. The reversible complexation with either strong or Lewis acids allowed us to characterize the electronic properties of the oligomers in different conformations (red ↔ blue). An approximate structural model consistent with the experimental data (X-ray diffraction) is presented and discussed. The energy gaps (close to 2 eV) indicated a fully conjugated structure for the oligomers. Electronic localization effects are detected in the terms of the series with the longest thienylenic sequence, therefore indicating the realization of a quantum-dot polymeric structure. χ(3) values observed under resonance conditions are about 10−9 e.s.u.