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Bibliografia
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Keywords
MOLECULAR BEAMS, COMPLEXES, MASS SPECTROMETRY, AB INITIO CALCULATIONS, CHIRALITY, HELICENES, CIRCULAR DICROISM, NANOAGGREGATES, LASER ABLATION

From free molecules to complexes and nanoaggregates: structure, chirality, reactivity and theory

Università degli Studi "G. d'Annunzio" Chieti-Pescara
Abstract
The research activity of this project is focused on the need to develop a deeper understanding of the geometry, electronic structure and reactivity of complexes and nanoaggregates through studies involving spectroscopy, ion-molecule chemistry, and electronic structure calculations. One of the main goals of this project is to achieve detailed information on the geometric and energetic factors governing the covalent and non-covalent aggregation of basic units, molecules and ions, to complexes and nanoaggregates in order that their formation could be more clearly understood and ultimately controlled.
To this aim we have brought together a multidisciplinary team whose expertise covers the areas of chemical physics, organic chemistry, gas-phase spectroscopy, reaction dynamics, ion-molecule chemistry, and electronic structure theory.
The project is framed around five activities, and various tasks and milestones were associated with each of these. Each activity is associated with an homogeneous class of investigative approaches, considered properties, or methods of production, rather than a specific type of complexes or nanostructures. As a result, the research findings can be applied to a number of different systems, where complexes and nanostructures play fundamental roles, such as key intermediates in electrophilic and nucleophilic aromatic substitution reactions, prosthetic groups or metal-porphyrin complexes whose investigation may allow insights into the details >>>

Principal Investigator
Nazzareno Re Università degli Studi "G. d'Annunzio" CHIETI-PESCARA
Research Objectives
The research activity of this project is focused on the need to develop a deeper understanding of the geometry, electronic structure and reactivity of complexes and nanoaggregates through studies involving spectroscopy, ion-molecule chemistry, and electronic structure calculations. One of the main goals of this project is to achieve detailed information on the geometric and energetic factors governing the covalent and non-covalent aggregation of basic units, molecules and ions, to complexes and nanoaggregates in order that their formation could be more clearly understood and ultimately controlled.
To this aim we have brought together a multidisciplinary team with experience and expertise in chemical physics, organic chemistry, gas-phase spectroscopy, reaction dynamics, ion-molecule chemistry, and electronic structure theory. By the term complex in the present context we refer to species that are formed from the encounter of two or more components. Complexes may thus be formed en route from reactants to products in a chemical reaction but may also be the end product of a simple association reaction or the starting material for the growth of nanostructures. A paramount factor affecting molecular recognition and binding in both macroscopic and microscopic systems is chirality and its important role in life science is widely testified.
By combining the expertise of the research groups involved in the project we plan to fill the gap between a purely experimental and >>>

Timescale
24 months
National and international background
Molecular complexes and the factors that govern their formation, properties and structures in the gas phase have received a great deal of attention in recent years.[1,2] Complexes may be formed en route from reactants to products in a chemical reaction but may also be the end products of a simple association reaction or the starting material for the growth of nanostructures. Spectroscopic and kinetic studies on these complexes provide valuable information about the nature and the strength of the interaction forces between their building units. Data on the formation and stability of larger clusters are of paramount importance to explain and predict not only the growth of nanostructures but also more complex phenomena such as phase transition, nucleation, development of surfaces and finally of bulk materials. Many studies on complexes and clusters were feasible because their synthesis could be easily performed in supersonic molecular beams. Specific information on the energetics, dynamics and structure of these species has been obtained by coupling the supersonic beams with laser studies, sophisticated mass spectrometry techniques (ESI-FT-ICR, ESI-MSn, MALDI-TOF) and spectroscopic apparatuses (REMPI).[1-3]
Benchmark complexes that play a key role in ion-molecule reactivity both in solution and in the gas phase can be obtained from simple aromatic molecules. Cationic sigma complexes or arenium ions are well recognized intermediates in electrophilic aromatic substitution >>>