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We present the determination of the conformational properties ofaeroplysinin-1 in aqueous solution by means of a combined experimentaland theoretical Raman optical activity (ROA) and vibrational circulardichroism (VCD) study. Aeroplysinin-1 is an antiangiogenic drug extractedfrom the sponge Aplysina cavernicolawhich has beenproved to be a valuable candidate for the treatment of cancer andother antiangiogenic diseases. Our study shows that this moleculepossesses the 1S,6Rabsolute configurationin aqueous solution, where only two conformers are present to a significantlevel. We discuss in detail the relationships between the chiro-opticalROA and VCD features, and the structural properties of various energyaccessible conformers are described. The present work is one of thefirst studies in which both ROA and VCD have been used as complementarytools for the determination of absolute configuration and dominantsolution-state conformations of an unknown therapeutically significantmolecule. [ABSTRACT FROM AUTHOR]

An analysis is performed on the molecular and electronic features in a series of trigonal molecules constituted by a central truxene core which is ramified with three oligofluorene moieties of different lengths. Arms and core are studied independently and upon threefold unification. Special emphasis is paid to the modulation of the conjugational properties in relation to substitution, molecular dimension, ring aromaticity, intermolecular forces, oxidation state, etc. Raman and optical absorption/emission spectroscopies in conjunction with computational theoretical results are combined for this purpose. The evolution of some key intensity ratios in the Raman spectra (i.e., I1300/I1235) is followed as an indication of electronic interaction between the core and the branches. The changes of the electronic delocalization upon solvation, with varying temperature in the solid state, with the nature of the aromatic unit (bithiophene/fluorene) or after electrochemical oxidation are interpreted. The modulation of the optical properties on the basis of the structure and energetics of the orbital around the gap is also addressed. Density functional theory was used to assign the vibrational and electronic spectra. [ABSTRACT FROM AUTHOR]

The molecular and electronic structures of a series of all-meta-substituted phenylacetylene mesitylenes peripherally substituted with donor or acceptor (D−A) groups are studied. The impact of meta- and para-substitution patterns is also analyzed by employing Raman and optical spectroscopies in conjunction with theoretical calculations. Outer phenyl rings display a partial quinoid character induced by two different motifs:  (i) outer phenyls → triple bond charge transfer for the cases where these phenyls are substituted with electron-donors; (ii) double electron withdrawing effect in the molecules with the peripheral phenyls substituted with electron acceptors. A moderate tuning of the optical gap is observed in agreement with the partial blockade of -electron conjugation exerted by the metadisposition. The orbital structure of the compounds partially preserves that of the mesitylene group showing extra-conjugation due to the addition of the arms, so that conjugation is not entirely obstructed but partially impeded in the ground electronic state (i.e., electron occupied orbitals). As for the excited states, the low-lying energy empty orbitals offer better conditions for full conjugation over the whole molecular scaffold. Interesting optical properties such as overlapping centers along the lowest energy optical excitations and enhanced optical transparency with importance for the application of these materials in optoelectronics have been justified on the basis of the electronic structure. A greater degree of quinoidization, and more allowed -electron delocalization, over the entire molecule is recognized in the case of linear phenylacetylenes substituting in parapositions the central core. [ABSTRACT FROM AUTHOR]

In this work, the interactions between heteroatoms (S, Se, and Te) and conjugated skeletons are analyzed. The study is carried out by using electronic absorption and fluorescence spectroscopies, electrochemistry, vibrational Raman spectroscopy, and theoretical calculations in the framework of DFT and TD−DFT theories. Optical spectra are described in terms of one-electron promotions between orbitals around the energy gap. Electrochemistry, in the framework of the Koopman's approach, is also interpreted. The vibrational Raman spectra are assigned to molecular modes and the evolution changing the heteroatom is addressed and an effective tuning of these properties is found. Part of this modulation is associated with local electronic interactions depending on the relative S, Se, and Te electronegativities. Unconventional long-range heteroatom−heteroatom interactions have been proposed which arise from the existence of effective π-conjugated channels. The molecular level understanding of structure−property relationships in these organic/inorganic semiconductors are of great interest in the interdisciplinary area of material science. [ABSTRACT FROM AUTHOR]