molecular orbital calculations; metal-organic materials; X-ray diffraction; coordination polymers; electron density distribution; distributed atomic polarizabilities
Tiana Davide, Francisco Evelio, Macchi Piero, Sironi Angelo, Martin Pendas Angel (2015), An Interacting Quantum Atoms analysis of the Metal-Metal Bond in [M2(CO)8]n Systems, in Journal of Physical Chemistry A
, 119, 2153-2160.
Dos Santos Leonardo H. R., Krawczuk Anna, Macchi Piero (2015), Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates, in Journal of Physical Chemistry A
, 119, 3285-3298.
Alemany Pere, Canadell Enric, Geng Yang, Hauser Jürg, Macchi Piero, Krämer Karl, Decurtins Silvio, Liu Shi-Xia (2015), Exploring the Electronic Structure of an Organic Semiconductor Based on a Compactly Fused Electron Donor-Acceptor Molecule, in ChemPhysChem
Macchi Piero, Gillet Jean-Michel, Taulelle Francis, Campo Javier, Claiser Nicolas, Lecomte Claude (2015), Modelling the experimental electron density: only the synergy of various approaches can tackle the new challenges, in IUCrJ
Ayers P. W., Boyd R. J., Bultinck P., Caffarel M., Carbo-Dorca R., Causà M., Cioslowski J., Contreras-Garcia J., Cooper D. L., Coppens P., Gatti C., Grabowski S., Lazzeretti P., Macchi P., Martin Pendas A., Popelier P. L. A., Ruedenberg K., Rzepa H., Savin A., Sax A., Schwarz W. H. E., Shahbazian S., Silvi B., Sola M., Tsirelson V. (2015), Six Questions on Topology in Theoretical Chemistry, in Comput. Theo. Chem.
, 1053, 2-16.
Krawczuk Anna, Macchi Piero (2015), The Polarizability of Organometallic bonds, in Comput. Theo. Chem.
, 1053, 165-172.
Krawczuk Anna, Macchi Piero (2014), Charge density analysis for crystal engineering, in Chemistry Central Journal
, 8, 68.
Macchi Piero (2014), Crystallographic approaches for the investigation of molecular materials: structure property relationships and reverse crystal engineering., in Chimia
, 68, 31-37.
Calahorro A. J., Macchi P., Salinas-Castillo A., San Sebastián E., Seco J. M., Rodríguez-Diéguez A. (2014), Photoluminescence of the First Examples of Metal-Organic-Frameworks with Two Novel Tetrazolatephenyl Acetic Acid Derivatives. An Experimental and Theoretical Study., in CrystEngComm
, 16, 10492-10496.
Krawczuk Anna, Perez Daniel, Macchi Piero (2014), PolaBer: a program to calculate and visualize distributed atomic polarizabilities based on electron density partitioning, in Journal of Applied Crystallography
, 47, 1452.
Rezende Dos Santos Leonardo Humberto, Genoni Alessandro, Macchi Piero (2014), Unconstrained and X-ray constrained Extremely Localized Molecular Orbitals: analysis of the reconstructed electron density, in Acta Crystallographica, section A
, A70, 532-551.
Chimpri Abita S., Gryl Marlena, Rezende dos Santos Leonardo Humberto, Krawczuk Anna, Macchi Piero (2013), Correlation between accurate Electron density and Linear Optical Properties in Amino acid derivatives: L-Histidinium Hydrogen Oxalate, in Crystal Growth & Design
Chimpri Abita S, Macchi P (2013), Electron density building block approach for metal organic frameworks, in Physica Scripta
, 87, 048105.
Macchi Piero (2013), Modern charge density studies: the entanglement of experiment and theory, in Crystallographic Reviews
, 19, 58-101.
This project is a continuation of the previous project 200021_125313, aimed at correlating the observable properties of hybrid metal organic materials and their ground state electron density distribution. The first steps were undertaken to test the most reliable and transferable electron density models for building blocks of these kinds of materials, in particular analyzing the coordinative bonds between the organic linkers and the metal connectors, and to study properties derived from the electron density distribution. The project merges theoretical investigations of isolated building blocks, simulations of their aggregation in crystals and experimental validation through accurate X-ray diffraction. In layered or three-dimensional framework materials, the modeling allows addressing the sites more keen to bind guest molecules (for example an absorbed gas, or an ion), by mapping the total interaction between host framework and guest, including electrostatic and non-electrostatic (dispersive) interactions. This put the bases for additional investigations that are proposed through this renewal: a) using ground state electron density to evaluate properties, for example susceptivities, useful for prediction of optical response of a material; b) using the building block modeling to carry out dynamic simulations, for example to predict and understand sorption processes; c) investigating some recent types of metal organic materials, based on zwitterionic amino acids as linkers, hence able to invert the charge of the host hybrid framework (cationic, instead of neutral or anionic).These goals can be achieved, using the approach previously developed, which is based on theoretical modeling of the building blocks (which are stable ions or neutral molecules), and transfer their electron density in the actual hybrid materials, which are usually more difficult to model from first principles (systems are often too big) or from experiments (single crystal samples often do not match the expected quality). The same approach could be used to simulate the dynamics of guest molecules in the host framework. The advantage of this treatment is the accurate evaluation of electrostatic energy, without high computational costs. In addition, some recent work proved that distributed polarizabilities based on electron density approaches are reliable and highly transferable, which could provide a more accurate evaluation of induction and van der Waals energies in these materials and give access to evaluation of optical properties, with potential extension to non linear optics (when using hyper polarizabilities). Moreover, the local polarizability function could be used to map reactive sites in a metal-organic material.In this project, we also propose to study an intriguing class of metal amino acids materials, that have several advantages: a) availability and costs; b) water based chemistry; c) homo-chirality and inverted charge of the framework; d) versatile coordination modes of the linker.This research could impact the scientific community operating in the field of supramolecular chemistry, because of the availability of new tools to perform crystal engineering.