Axial Coordinated Manganese(III) Porphyrin/Tetraazaporphyrin - 4-(10-phenylanthracen-9-yl)Pyridine Dyads: Self-Assembly, Structure and Spectral Properties in Ground and Excited States.

Self-assembly of new donor-acceptor systems based on (5,10,15,20-tetraphenylporphinato)manganese(III)/(5,10,15,20-tetra-4-tert-butylphenylporphinato)manganese(III)/(octakis(4-tert-butylphenyl)tetraazaporphinato)manganese(III) acetate ((AcO)MnTPP/(AcO)MnTBPP/(AcO)MnTAP) and 4-(10-phenylanthracen-9-yl)pyridine (PyAn) was studied using fluorescence spectroscopy and mass spectrometry. It was found that the coordination complexes of 1 : 1 composition (dyads) are formed in toluene. The spectral properties, the chemical structures and redox behavior of the dyads were described using 1H NMR, IR, ESR spectroscopy and cyclic voltammetry, respectively. The dynamic processes and the characteristics in the excited state of the dyads were obtained using the femtosecond transient absorption spectroscopy method. Density functional theory (DFT), time-dependent DFT methods were used to elucidate the dyad electronic structures and to establish the differences in their frontier molecular orbitals. The analysis of the lambda parameter and the distance of hole-pair interaction was indicated more favorable charge transfer between the macrocycle and the axial PyAn fragment in (AcO)(PyAn)MnTAP. The calculated values of the zero-field splitting parameters D and E/D, together with the g tensors of the lowest spin-orbit state for (AcO)MnTPP and (AcO)(PyAn)MnTPP were obtained using the combination of DFT and Multireference Perturbation Theory (CASSCF/NEVPT2) simulations. The data obtained develop the fundamental basis in the field of photovoltaics and show the prospects for the study of molecular systems of this class.

Alkylimidazolium Protic Ionic Liquids: Structural Features and Physicochemical Properties.

We focus on a series of protic ionic liquids (PILs) with imidazolium and alkylimidazolium (1R3HIm, R=methyl, ethyl, propyl, and butyl) cations. Using the literature data and our experimental results on the thermal and transport properties, we analyze the effects of the anion nature and the alkyl radical length in the cation structure on the above properties. DFT calculations in gas and solvent phase provide further microscopic insights into the structure and cation-anion binding in these PILs. We show that the higher thermodynamic stability of an ion pair raises the PIL decomposition temperature. The melting points of the salts with the same cation decrease as the hydrocarbon radical in the cation becomes longer, which correlates with the weaker ion-ion interaction inthe ion pairs. A comparative analysis of the protic ILs and corresponding ILs (1R3MeIm) with the same radical (R) in the cation structure and the same anion has been performed. The lower melting points of the ILs with 1R3MeIm cations are assumed to result from the weakening of both the ion-ion interaction and the hydrogen bond.

Polymorphic forms of antiandrogenic drug nilutamide: structural and thermodynamic aspects.

Attempts to obtain new cocrystals of nonsteroidal antiandrogenic drug nilutamide produced alternative polymorphic forms of the compound (Form II and Form III) and their crystal structures were elucidated by single-crystal X-ray diffraction. Apart from the cocrystallization technique, lyophilization was found to be an effective strategy for achieving polymorph control of nilutamide, which was difficult to obtain by other methods. The physicochemical properties and relative stability of the commercial Form I and newly obtained Form II were comprehensively investigated by a variety of analytical methods (thermal analysis, solution calorimetry, solubility, and sublimation), whereas for Form III, only a handful of experimental parameters were obtained due to the elusive nature of the polymorph. Form I and Form II were found to be monotropically related, with Form I being confirmed as the thermodynamically most stable solid phase. In addition, the performance of different DFT-D and semi-empirical schemes for lattice energy calculation and polymorph energy ranking was compared and analysed. Lattice energy calculations using periodic DFT at B3LYP-D3/6-31(F+)G(d,p) and PBEh-3c/def2-mSVP levels of theory were found to provide the most accurate lattice energy values for Form I against experimental data, while PIXEL and PBEh-3c/def2-mSVP were the only methods that predicted the correct order of stability of Forms I and II.

Magnetic resonance and Mössbauer studies of superparamagnetic γ-Fe2O3 nanoparticles encapsulated into liquid-crystalline poly(propylene imine) dendrimers.

We present the first results of electron magnetic resonance (EMR) and Mössbauer spectroscopy studies of γ-Fe(2)O(3) nanoparticles (NPs) incorporated into liquid-crystalline, second-generation dendrimers. The mean size of NPs formed in the dendrimers was around 2.5 nm. A temperature-driven transition from superparamagnetic to ferrimagnetic resonance was observed for the sample. Low-temperature blocking of the NP magnetic moments has been clearly evidenced in the integrated EMR line intensity and the blocking temperature was about 60 K. The physical parameters of magnetic NPs (magnetic moment, effective magnetic anisotropy) have been determined from analyses of the EMR data. The effective magnetic anisotropy constant is enhanced relative to bulk γ-Fe(2)O(3) and this enhanced value is associated with the influence of the surface and shape effects. The angular dependence of the EMR signal position for the field-freezing sample from liquid-crystalline phase showed that NPs possessed uniaxial anisotropy, in contrast to bulk γ-Fe(2)O(3). Mössbauer spectroscopy determined that fabricated NPs consisted of an α-Fe core and a γ-Fe(2)O(3) shell.