Publications

Abstract This work presents a comprehensive study exploring the thermodynamics of the solid phase of a series of phenylimidazoles, encompassing experimental measurements of heat capacity, volatility, and thermal behavior. The influence of successive phenyl group insertions on the imidazole ring on thermodynamic properties and supramolecular behavior was thoroughly examined through the evaluation of 2-phenylimidazole (2-PhI), 4-phenylimidazole (4-PhI), 4,5-diphenylimidazole (4,5-DPhI), and 2,4,5-triphenylimidazole (2,4,5-TPhI). Structural correlations between molecular structure and thermodynamic properties were established. Furthermore, the investigation employed UV-vis spectroscopy and quantum chemical calculations. Additive effects arising from the introduction of phenyl groups were found through the analysis of the solid-liquid and solid-gas equilibria, as well as heat capacities. A good correlation emerged between the thermodynamic properties of sublimation and the molar volume of the unit cell, evident across 2-PhI, 4,5-DPhI, and 2,4,5-TPhI. In contrast to its isomer 2-PhI, 4-PhI exhibited greater cohesive energy due to the stronger N-HN intermolecular interactions, leading to the disruption of coplanar geometry in the 4-PhI molecules. The observed higher entropies of phase transition (fusion and sublimation) are consistent with the higher structural order observed in the crystalline lattice of 4-PhI.

Abstract This work reports the thermodynamic and morphological study and characterization of four salts consisting of a divalent/trivalent cobalt complex with pyrazole-pyridine ligands (FK 102 and FK 209 samples) and bis(trifluoromethylsulfonyl)imide (TFSI) moieties as counter anions. The oxidation state of the central metal (Co(II) or Co(III)) and the presence of tert-butyl (t-Bu) groups in the ligand structure were found to have a strong impact on the thermal behavior, phase stability, heat capacities, and thin-film morphology of each salt. The Co(II) complexes exhibited good thermal stability up to 600 K. Lower thermal stability was observed for the Co(III) congeners. The FK 209 Co(III) displayed a higher melting temperature but a partial decomposition during or above melting was detected. The higher melting temperatures observed for the Co(III) complexes were found to be entropically driven. However, the addition of t-Bu in the ligand (FK 209) leads to an increase in the melting temperature, which is driven by the enthalpy of fusion. The four compounds studied evidenced a large glass-forming ability. Moreover, the thermal stability of the glassy state was clearly increased when the ligands comprised t-Bu groups. The contribution of the t-Bu group for the molar heat capacity in the solid phase, at T = 298.15 K, was found to be (110 ± 3) J·K−1·mol−1 and (98 ± 4) J·K−1·mol−1 for the Co(II) and Co(III) complexes, respectively. These results are in good agreement with the contribution of the t-Bu group observed for both solid and liquid phases in other materials, indicating that the t-Bu groups are relatively unhindered in the crystalline phase of the salts. The morphological behavior of the thin films of FK 102 samples was found to be quite similar to the observed for typical ionic liquids, with the formation of micro- and nanodroplets onto different substrates. The introduction of t-Bu substituents in the ligand structure was found to have a strong impact on the formation of homogeneous and compact nanofilms for the FK 209 salts. © 2022 Elsevier Ltd

Abstract This work reports a comprehensive experimental evaluation of the solid-liquid-gas phase equilibria for five representative phenylene-thiophene co-oligomers (3-ring aromatic compounds having both phenyl and thienyl units). The melting temperatures and corresponding standard molar enthalpies and entropies of fusion were measured by differential scanning calorimetry. The equilibrium vapor pressures of the crystalline solids as a function of temperature were measured by a combined Knudsen/quartz-crystal effusion method, with the consequent derivation of the standard molar enthalpies, entropies, and Gibbs energies of sublimation. The thermodynamic properties of vaporization were estimated from the fusion and sublimation data. The results were analyzed together with the literature data for the corresponding phenylene and thiophene homo-oligomers. The thermodynamic properties of fusion and sublimation exhibited a dependence on ring identity and position that cannot be adequately described by a simple group additivity reasoning. The plot of the Gibbs energy of sublimation as a function of the number of thienyl rings in the co-oligomer showed the existence of two series. Terminal 3-thienyl rings and a linear molecular shape were found to be consistent factors contributing to the stabilization of the crystal phase. The higher melting temperatures and lower volatilities of crystalline 3-thienyl compounds were tentatively explained by the ability of these rings to maximize intermolecular C-H & BULL;& BULL;& BULL;pi interactions independently of the sulfur position. The optical energy gaps, as measured by UV-vis in solution, were found to lie within the values for typical organic semiconductors (< 4 eV) and to decrease for co-oligomers containing more 2-thienyl units, following the increased ring-ring planarity of the molecules. The surface morphology of vapor-deposited thin films suggests a stronger tendency of the co-oligomers, if compared to their corresponding homo-oligomers p-terphenyl and terthiophene, to form less amorphous films.

Abstract Ionic liquids (ILs) have been widely used for energy storage and conversion devices due to their negligible vapor pressure, high thermal stability, and outstanding interfacial properties. Notably, the interfacial nanostructure and the wettability of thin ionic liquid films on solid surfaces are of utmost relevance in nanosurface science and technology. Herein, a reproducible physical vapor deposition methodology was used to fabricate thin films of four alkylimidazolium bis(trifluoromethylsulfonyl)imide ILs. The effect of the cation alkyl chain length on the wettability of ILs was explored on different surfaces: gold (Au); silver (Ag); indium-tin oxide (ITO). High-resolution scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to evaluate the morphology of the produced micro- and nanodroplets and films. SEM and AFM results revealed an island growth for all the ILs deposited on ITO and Ag surfaces, with a lower minimum free area to promote nucleation (MFAN) in Ag and higher wettability for ILs having larger non-polar domains. The low wettability of ITO by the studied ILs was highlighted. For long-chain ILs, nucleation and growth mechanisms were strongly conditioned by coalescence processes. The results also supported the higher affinity of the ILs to the Au surface. The increase in the length of the cation alkyl chain was found to promote a better film adhesion inducing a 2D growth and higher wetting ability.

Abstract This study investigates the nucleation and growth of micro-/nanodroplets of triflate-based ionic liquids (ILs) fabricated by vapor deposition on different surfaces: indium tin oxide (ITO); silver (Ag); gold (Au). The ILs studied are constituted by the alkylimidazolium cation and the triflate anion-[CnC1 im][OTF] series. One of the key issues that determine the potential applications of ILs is the wettability of surfaces. Herein, the wetting behavior was evaluated by changing the cation alkyl chain length (C-2 to C-10). A reproducible control of the deposition rate was conducted employing Knudsen cells, and the thin-film morphology was evaluated by high-resolution scanning electron microscopy (SEM). The study reported here for the [C(n)C(1)im][OTF] series agrees with recent data for the [C(n)C(1)im][NTf2] congeners, highlighting the higher wettability of the solid substrates to long-chain alkylimidazolium cations. Compared to [NTf2], the [OTF] series evidenced an even more pronounced wetting ability on Au and coalescence processes of droplets highly intense on ITO. Higher homogeneity and film cohesion were found for cationic groups associated with larger alkyl side chains. An island growth was observed on both Ag and ITO substrates independently of the cation alkyl chain length. The Ag surface promoted the formation of smaller-size droplets. A quantitative analysis of the number of microdroplets formed on Ag and ITO revealed a trend shift around [C(6)C(1)im][OTF], emphasizing the effect of the nanostructuration intensification due to the formation of nonpolar continuous domains.

Abstract The thermodynamic properties and band gap energies were evaluated for six ortho- and peri-fused polycyclic aromatic hydrocarbons (PAHs): triphenylene; benzo[a]pyrene; benzo[e]pyrene; perylene; benzo[ghi]perylene; coronene. The standard molar enthalpies of formation in the crystalline state and the standard molar enthalpies of sublimation were measured by high precision combustion calorimetry and Knudsen effusion methodology, respectively. The combination of the molar enthalpies of formation in the crystalline state with the respective enthalpies of sublimation was used to evaluate the energetics of the progressive peri-fusion of the aromatic moieties from triphenylene to coronene aiming to investigate the hypothetical superaromaticity character of coronene. The linear trend of the enthalpy of formation in crystalline and gaseous phases in the series (from benzo[e]pyrene to coronene) is an irrefutable indication of a non-superaromaticity character of coronene. High accurate thermodynamic properties of sublimation (volatility, enthalpy, and entropy of sublimation) were derived by the measurement of vapor pressures as a function of temperature, using a Knudsen/quartz crystal effusion methodology. Furthermore, the p-electronic conjugation of these compounds was explored by evaluation of the optical band gaps along with this series of compounds. The morphology of perylene, benzo[ghi]perylene, and coronene thin films, deposited by physical vapor deposition onto transparent conductive oxide substrates (ITO and FTO), was used to analyze the nucleation and growth mechanisms. The morphologies observed were found to be related to the cohesive energy and entropy of the bulk.

Abstract The impact of structural differentiation between phenylcarbazoles (PhC, mCP, CBP, TCB) and phenylamines (TPA, BDB, TPB, TDAB) on the phase equilibria, optical spectrum, band gap, and thin-film morphology is evaluated and discussed. The carbazolyl units lead to a lower electronic conjugation contributing to a wide band gap when compared with the diphenylamine analogs. The fusion and sublimation equilibria indicate that entropic contribution is the key factor for the distinguished melting behavior and solid-phase volatility between phenylcarbazole derivatives and phenylamine analogs. The molecular differentiation between the two classes of compounds is not reflected in the crystal packing and intermolecular interactions. However, compared with the diphenylamino groups, the incorporation of carbazolyl moieties contributes to a less flexible molecule. Moreover, the results evidence that intermolecular bonding disruption along the fusion transition is more extensive for phenylamine derivatives. Due to the asymmetric nonplanar structure, mCP is characterized by a ratio of {T-g/T-m approximate to 3/4} while the more symmetric CBP and TCB molecules display ratios closer to {T-g/T-m approximate to 2/3}. Vapor-deposited thin films of mCP, CBP, and TCB are amorphous and their morphology is highly dependent on the substrate roughness. The lower flexibility of nonplanar phenylcarbazoles induces the formation of a glassy state due to the harder packing mechanism leading to the lower ability of the crystallization process.

Abstract In this study, a homogeneous thin film growth of pentacene onto indium tin oxide (ITO) coated glass surfaces is explored using a high-resolution and reproducible vapor deposition methodology. Moreover, vacuum thermal evaporation of ionic liquids (ILs) ([C(2)C(1)im][NTf2] and [C(2)C(1)im][OTF]) onto ITO, gold/palladium (AuPd) and pentacene surfaces were performed. A greater wettability behavior of ILs is observed for surfaces containing AuPd. Sequential and simultaneous depositions of ILs and pentacene were explored. Simultaneous depositions lead to the formation of nanocomposites films, consisting of IL micro- and nanodroplets covered by pentacene layers. Plasma surface treatment was used to induce the ILs droplets coalescence and explore the dynamics and phase separation of the nanocomposites. The [C(2)C(1)im][OTF] droplets were found to be completely covered with pentacene, which suggests a great affinity between cation-anion pairs and the aromatic moiety. Pentacene films and their nanocomposites with ILs exhibit a typical optical band gap ofE(gap)=1.77 eV, indicating that the nanocomposite phase domains are large enough to behavior as the bulk.

Abstract The chain-length dependence of the thermodynamic properties associated with the solid-to-liquid, liquid-to-gas, and solid-to-gas phase equilibria is analyzed and discussed for homologous families of linear alpha,omega-disubstituted alkanes, R-(CH2)(n)-R series. A remarkable alternation on the melting properties exhibited by even and odd-numbered alkanes is clearly emphasized in their a,w-disubstituted derivatives since the even members display increased properties due to their higher crystal packing density. The odd-even effect is also perceived in the values of Delta H-sub degrees and Delta S-sub degrees. Strong hydrogen bonding contributes to high boiling points and Delta H-vap degrees values evidenced by alkane-alpha,omega-diols. Moreover, the anomalously low values of Delta H-sub degrees and Delta H-vap degrees reported for larger dicarboxylic acids suggest the formation, in the vapor phase, of hydrogen-bonded cyclic structures. Furthermore, the analysis of the Delta H-fus degrees/Delta H-sub degrees and Delta S-sub degrees/Delta S-sub degrees ratios is used to highlight the contribution of functional groups to the cohesive interaction preserved in the liquid phase after a fusion transition. The thermodynamic interpretation indicates a higher structuration in the liquid alkane-alpha,omega-diols and alkane-alpha,omega-dioic acids, which have lower ratios of Delta H-fus degrees/A(sub)H degrees than corresponding n-alkanes. In addition, the thermodynamic analysis supports that hydrogen bonding in the liquid phase of alkanamines or alkane-alpha,omega-diamines has a significant low contribution to the overall intermolecular interactions.

Abstract Nanoscience and technology has generated an important area of research in the field of properties and functionality of ionic liquids (ILs) based materials and their thin films. This work explores the deposition process of ILs droplets as precursors for the fabrication of thin films, by means of physical vapor deposition (PVD). It was found that the deposition (by PVD on glass, indium tin oxide, graphene/nickel and gold-coated quartz crystal surfaces) of imidazolium [C(4)mim][NTf2] and pyrrolidinium [C(4)C(1)Pyrr][NTf2] based ILs generates micro/nanodroplets with a shape, size distribution and surface coverage that could be controlled by the evaporation flow rate and deposition time. No indication of the formation of a wettinglayer prior to the island growth was found. Based on the time-dependent morphological analysis of the micro/nanodroplets, a simple model for the description of the nucleation process and growth of ILs droplets is presented. The proposed model is based on three main steps: minimum free area to promote nucleation; first order coalescence; second order coalescence.