Manuela Ramos Silva

Market orientation and performance: modelling a neural network

Purpose – This paper aims to investigate the impact of market orientation (MO) on performance using a neural network model in order to find new linkages and new explanations for this relationship.Design/methodology/approach – This investigation is based on a survey data collection from a sample of 192 Portuguese companies. A neural network model has been developed to identify the effects of each dimension of MO on each dimension of performance.Findings – Relationship among MO and performance was corroborated but MOs impact is poor and based on its first dimension, market intelligence generation.Research limitations/implications – Further research in this field should be conducted using other tools offered by neural network modelling.Practical implications – Managers should give more attention to cross‐functional co‐ordination in order to improve market intelligence dissemination and responsiveness and, thus, global performance.Originality/value – The paper presents the development of a neural network mod...

Novel erbium(III) fluorinated β-diketonate complexes with N,N-donors for optoelectronics: from synthesis to solution-processed devices

Three novel ternary Er3+ complexes emitting in the C band transmission window for fiber optic communications have been synthesised and their structures have been elucidated by single crystal X-ray diffraction. The fluorinated β-diketonate ligand, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, combines a good absorption cross-section in the ultraviolet region with reduction of non-radiative quenching of the Er3+ emission, while the rigidity and bulkiness of the three different N,N-donors (2,2′-bipyridine, bathophenanthroline and 5-nitro-1,10-phenanthroline) have a pronounced impact on the emission intensity of luminescence. Furthermore, the choice of the ancillary ligand also determines the efficiency of the antenna effect, leading to complete quenching of the ligand-associated visible emission for the optimized complex with 5-nitro-1,10-phenanthroline. Solution processed 1.54 μm organic light-emitting diodes have been manufactured and characterized for this complex, confirming the aforementioned complete resonant energy transfer from the ligands to the Er3+ ion. The features of the reported device fabrication show a simple way to obtain large area NIR-OLEDs.

Self-assembled liquid crystals by hydrogen bonding between bipyridyl and alkylbenzoic acids: solvent-free synthesis by mechanochemistry

A series of thermotropic hydrogen-bonded liquid crystalline structures based on 4,4′-bipyridyl and aliphatic carboxylic acids was prepared by a mechanosynthesis technique. This series was characterised by polarising optical microscope, differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray powder diffraction and 1H NMR relaxometry experimental techniques. In these complexes, the bipyridyl component, a non-mesogenic substance by itself, acts as a double H-bond acceptor, whereas the alkylbenzoic acid acts as a H-bond donor, in a 1:2 proportion. The so-formed complexes exhibit mesophases that are not observed by the single components. A characteristic phase (smectic A) is identified and shown to be affected by the alkyl chain length. The isotropisation temperature is increased by the supramolecular aggregation through the H-bonds.

Structure and NIR-luminescence of ytterbium(III) beta-diketonate complexes with 5-nitro-1,10-phenanthroline ancillary ligand: assessment of chain length and fluorination impact

Seven new tris(β-diketonear-nate)ytterbium(III) complexes with the general formula [Yb(β-diketonate)3(5NO2phen)] (where the β-diketone is either 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione, 2,4-hexanedione or 2,6-dimethyl-3,5-heptanedione, and 5NO2phen = 5-nitro-1,10-phenanthroline) were synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Single crystal X-ray structures have been determined for three fluorinated complexes and ground state geometries of the other four complexes have been predicted using the Sparkle/PM6 model. These experimental structures and those designed by semi-empirical models reveal octacoordination around the Yb(3+) ion. Photoluminescence studies and lifetime measurements show that the increase in the fluorinated β-diketonate chain length is associated with a decrease in Yb(3+) luminescence intensity of the (2)F5/2→(2)F7/2 transition at around 980 nm and the (2)F5/2 excited state lifetime, while the ligand lifetime value remains almost unaffected. Finally, fluorination of the ligands is only advised when the complexes are to be used for co-doping with isostructural Er(3+) complexes for optical amplifiers, since it leads to a slight decrease in luminescence intensity for the same β-diketonate chain length.

Amplification of the linear and nonlinear optical response of a chiral molecular crystal

We have observed large second-order nonlinear optical and vibrational circular dichroism (VCD) responses in a charge-transfer-type L-Histidinium salt. Using X-ray Diffraction, VCD spectroscopy, and time-dependent density functional theory to characterize the compound, we employ a two-level model to explain and quantify the strongly enhanced optical signals. We find that both linear and nonlinear optical responses are greatly enhanced by a single low-lying charge-transfer state.

X-ray and deuterium labeling studies on the abnormal ring cleavages of a 5β-epoxide precursor of formestane

A new convergent synthesis of the antitumor steroid formestane (4-OHA) 5 has been performed from the easily available epimeric mixture of 5 alpha- and 5 beta-androst-3-en-17-one 1a and 1b in order to attempt a yield improvement. A two-step oxidative route followed by base-catalyzed isomerization was applied to the 5 alpha- and 5 beta-epimers 1a and 1b, either as a mixture or separately, leading to the title compound 5. From epimer 1a an efficient process was attained to prepare the desired aromatase inhibitor formestane. Epimer 1b led to the formation of the same compound 5. Additionally, 1b have also been converted in 5 beta-hydroxyandrostane-3,17-dione 12 and androst-4-ene-3,17-dione 13, revealing an unexpected reactivity of the 3 beta,4 beta-epoxy-5 beta-androstan-17-one intermediate 6 formed from 1b during the first oxidative step with performic acid. Cleavage of the epoxide 6 led to the trans-diaxial and the trans-diequatorial vic-diols 7 and 8 and to the 1,3-diol 9. The formation of the abnormal products 8 and 9 were investigated through X-ray and deuterium labeling studies. Diol 8 was formed through a trans-diequatorial epoxide ring opening and the 1,3-diol 9 was formed through an intramolecular rearrangement involving a 1,2-hydride shift. All the vic-diols 3, 7 and 8 formed, proved to be good precursors for the synthesis of the target compound 5.

Cycloaddition reactions of 3-aryl-5-phenyl-5H, 7H-thiazolo[3,4-c]oxazol-4-ium-1-olates

Intermolecular 1,3-dipolar cycloaddition of (5R)- and (5S)-3,5-diphenyl-5H,7H-thiazolo[3,4-c]oxazol-4-ium-1-olates, (5R)- and (5S)-3-(p-methoxyphenyl)-5-phenyl-5H,7H-thiazolo-[3,4-c]oxazol-4-ium-1-olates with a range of dipolarophiles is described. New chiral 5-aryl-3-phenyl-1H,3H-pyrrolo[1,2-c]thiazoles with R and S configuration were obtained. The structure of methyl (3R)-3-phenyl-5-(p-methoxyphenyl)-1H,3H-pyrrolo[1,2-c]thiazole-6-carboxylate was determined by X-ray crystallography. The synthesis of 7,7a-dihydro-1H,3H-pyrrolo[1,2-c]thiazole-6,7-dicarboxylates was also achieved.

Strong hydrogen-bonded amino acid dimers in l-alanine alaninium nitrate

The title compound, C3H7NO2*C3H8NO2+*NO3-, contains L-alanine-alaninium dimers bonded via the carboxyl groups by a strong asymmetric hydrogen bond with an O...O distance of 2.4547 (19) A. The neutral alanine molecule exists as a zwitterion, where the carboxyl group is dissociated and the amino group is protonated. The alaninium cation has both groups in their acidic form. The alanine molecule and the alaninium cation differ only slightly in their conformation, having an N-C(alpha)-C=O torsion angle close to -25 degrees. The dimers and the nitrate anion are joined through a three-dimensional hydrogen-bond network, in which the full hydrogen-bonding capabilities of the amino groups of the two alanine moieties are realised.

Intermolecular Dipolar Cycloaddition Reactions of 5H,7H-Thiazolo[3,4-c]oxazol-4-ium-1-olates

Abstract (5R)-3-Methyl-5-phenyl-5H,7H-thiazolo[3,4-c]oxazol-4-ium-1-olate was generated in the presence of a range of dipolarophiles. The intermolecular 1,3-dipolar cycloaddition of this mesoionic species led to the synthesis of chiral 1H-pyrrolo[1,2-c]thiazole derivatives 7a, 7b, 8, 14, 18, 19 and 20. In the reaction with methyl and ethyl vinyl ketone, spiro compounds 9 and 15 were also obtained. The structure of compound 15 was determined by X-ray crystallography.

Crystal structure of hydrated diphenylguanidinium hexafluoroferrate (III)

Abstract The crystal structure of 3C13H14N3+FeF63−·3.5H2O was determined. Both phenyl rings of the diphenylguanidine cation are oriented syn to the central CNH2 group. The anions and cations are held together by a three-dimensional network of hydrogen bonds. In the synthesis of this compound, a second phase (iron trifluoride trihydrate) was formed and identified by powder diffraction data. Mossbauer results show two different iron environments compatible with the two phases reported.