Molecular Spectroscopy Group/Research

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Solid State Photoreactivity

[2+2] photocycloadditions

 Single-crystal-to-single-crystal (SCSC) transformations represent a wonderful mean to understand a solid state reaction evolution, as they link its progress to the crystal structural changes. The [2+2] cycloaddition of cinnamic acids are studied as topochemical model system by X-ray while our approach is to use vibrational spectroscopy (IR and Raman) to understand the mechanism which govern the transformation in the condensed phase. 

References:

  • The impact of solid solution composition on kinetics and mechanism of [2+ 2] photodimerization of cinnamic acid derivatives. L. Pandolfi, A. Giunchi, T. Salzillo, A. Brillante, R.G. Della Valle, E. Venuti, F. Grepioni, S. D'Agostino.CrystEngComm 23 (6), 1352-1359 (2021) 10.1039/D0CE01718C
  • Visualizing a SCSC [2 + 2] photodimerization through its lattice dynamics: an experimental and theoretical investigation. A. Giunchi, L. Pandolfi, T. Salzillo, A. Brillante, R.G. Della Valle, S. d’Agostino, E. Venuti. In preparation

[4+4] photocycloadditions

Photochemical reactions of anthracene derivatives have different mechanism that can be classified as topochemical, non-topochemical or reversible. By means of a micro-Raman technique, we are capable of monitoring, at the same time and on the very same spot, the molecular (intramolecular vibrations or internal motions) and the lattice (intermolecular vibrations or lattice phonons) transformations. Studying the delay between the molecular and the structural changes it is possible to gain information about the reaction path of the different photoreactive systems.

References:

  • Commenting on the photoreactions of anthracene derivatives in the solid state. T. Salzillo, A. Brillante. CrystEngComm 21 (20), 3127-3136 (2019) 10.1039/C9CE00176J
  • Crystal-to-crystal photoinduced reaction of dinitroanthracene to anthraquinone. T. Salzillo, I. Bilotti, R.G. Della Valle, E. Venuti, A. Brillante. Journal of the American Chemical Society 134 (42), 17671-17679 (2012) 10.1021/ja307088n
  • Micro Raman investigation of the photodimerization reaction of 9-cyanoanthracene in the solid state. T. Salzillo, S. Zaccheroni, R.G. Della Valle, E. Venuti, A. Brillante.The Journal of Physical Chemistry C 118 (18), 9628-9635 (2014) 10.1021/jp412484x

Polymorphism and Phase Transitions in Molecular Materials

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Charge Transfer Complexes

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