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Properties of metal-organic materials from accurate electron density determination

English title Properties of metal-organic materials from accurate electron density determination
Applicant Macchi Piero
Number 141271
Funding scheme Project funding (Div. I-III)
Research institution Departement für Chemie und Biochemie Universität Bern
Institution of higher education University of Berne - BE
Main discipline Physical Chemistry
Start/End 01.04.2012 - 31.03.2015
Approved amount 193'508.00
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Keywords (6)

molecular orbital calculations; metal-organic materials; X-ray diffraction; coordination polymers; electron density distribution; distributed atomic polarizabilities

Lay Summary (English)

Lead
Materials properties depend on the distribution of electrons. In this project, we correlate the observable electron density (measured experimentally or computed theoretically) and the respons of materials. For example, indexes of refraction of a crystal are calculated from the electron density partitioning of the dipole polarizability of a molecule. This enables to understand how the material property is generated from specific stereoelectronic features of the functionals groups and the bulding blocks.
Lay summary

In this project we correlate the observable optic/electronic properties of hybrid metal organic materials and their ground state electron density distribution in crystals.

The materials are modeled with a building blocks approach, where organic linkers, metal connectors and guest molecules are described in multipolar expansion. When this cannot be derived on the actual materials (because experiments cannot be sufficiently accurate or theoretical calculations are too demanding) the isolated building blocks are  simulated based on simple calculations on isolated building blocks, treating the aggregation in crystalline materials as a first order perturbation. 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.

In this project, reconstructed ground state electron density of the hybrid materials are used to evaluate properties, for example electric susceptibilities, useful for prediction of optical response of a material.

We have so far published the basic theoretical framework for the building block reconstruction of the crystal linear susceptibility. Application to a wider class of potentially useful optical materials is currently in due course and a publication has been submitted.

Among various materials, an appealing class is that of metal bio-organic frameworks, based on amino acids as linkers, able to produce a quite variable charge of the host hybrid framework (cationic, neutral or anionic depending on reaction conditions) and to infer specific properties to the materials based on their chirality.

We started this investigation by analyzing the amino acid linkers in their molecular crystals, in salts with another acid (e.g. oxalic acid) acting as proton donor and eventually in metal coordination polymers.

We have so far published results of the investigations in pure amino acids and in their salts. The M-BioF crystals are currently under investigation and further publication is in due course.

Direct link to Lay Summary Last update: 19.12.2014

Responsible applicant and co-applicants

Name Institute

Employees

Publications

Publication
An Interacting Quantum Atoms analysis of the Metal-Metal Bond in [M2(CO)8]n Systems
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.
Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates
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.
Exploring the Electronic Structure of an Organic Semiconductor Based on a Compactly Fused Electron Donor-Acceptor Molecule
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, 1361-1365.
Modelling the experimental electron density: only the synergy of various approaches can tackle the new challenges
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, 441-451.
Six Questions on Topology in Theoretical Chemistry
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.
The Polarizability of Organometallic bonds
Krawczuk Anna, Macchi Piero (2015), The Polarizability of Organometallic bonds, in Comput. Theo. Chem., 1053, 165-172.
Charge density analysis for crystal engineering
Krawczuk Anna, Macchi Piero (2014), Charge density analysis for crystal engineering, in Chemistry Central Journal, 8, 68.
Crystallographic approaches for the investigation of molecular materials: structure property relationships and reverse crystal engineering.
Macchi Piero (2014), Crystallographic approaches for the investigation of molecular materials: structure property relationships and reverse crystal engineering., in Chimia, 68, 31-37.
Photoluminescence of the First Examples of Metal-Organic-Frameworks with Two Novel Tetrazolatephenyl Acetic Acid Derivatives. An Experimental and Theoretical Study.
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.
PolaBer: a program to calculate and visualize distributed atomic polarizabilities based on electron density partitioning
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.
Unconstrained and X-ray constrained Extremely Localized Molecular Orbitals: analysis of the reconstructed electron density
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.
Correlation between accurate Electron density and Linear Optical Properties in Amino acid derivatives: L-Histidinium Hydrogen Oxalate
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, 2995-3010.
Electron density building block approach for metal organic frameworks
Chimpri Abita S, Macchi P (2013), Electron density building block approach for metal organic frameworks, in Physica Scripta, 87, 048105.
Modern charge density studies: the entanglement of experiment and theory
Macchi Piero (2013), Modern charge density studies: the entanglement of experiment and theory, in Crystallographic Reviews, 19, 58-101.

Collaboration

Group / person Country
Types of collaboration
Dr. Louis J. Farrugia Department of Chemistry, University of Glasgow Great Britain and Northern Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. Jamie Manson Easter Washington University United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
Prof. R. Ersnt Utah University United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
Dr. Alessandro Genoni, Université Lorraine France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. Angel Martin Pendas, University of Oviedo Spain (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Jagiellonian University (krakow) Poland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. Fabio Ragaini, University of Milano Italy (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Universidade Federal Fluminense Brazil (South America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
XDRAC Talk given at a conference Distributed atomic polarizabilities: a tool to identify efficient functional groups for high refractive index materials 27.02.2015 Salem, India Macchi Piero;
Asian Charge Density Workshop Talk given at a conference General Aspects of Multipolar Modelling 23.02.2015 Bangalore, India Macchi Piero;
intermolecular interactions Talk given at a conference Polarization of molecules induced by intermolecular interactions 20.05.2014 Nancy, France Macchi Piero;
Natta's seeds grow Talk given at a conference An approach toward reverse crystal engineering 21.11.2013 Milano, Italy Macchi Piero;
MISSCA 2013 Talk given at a conference Calculation of crystal optical properties from molecular electron density 09.09.2013 Como, Italy Macchi Piero;
Gordon Conference on electron Distribution and chemical bonding Poster Electron density distribution of Metal-Biomolecule Frameworks based on [ZnHPO3]n secondary building unit 02.06.2013 Les Diablerets, Switzerland Macchi Piero; Chimpri Abita Shyorotra; Lanza Arianna;
Gordon Conference on electron Distribution and chemical bonding Poster Atomic polarizability as a tool for predicting linear optical properties 02.06.2013 Les Diablerets, Switzerland Macchi Piero; Rezende dos Santos Leonardo Humberto;
Gordon Conference on electron Distribution and chemical bonding Poster Distributed atomic polarizabilities from Electron Density partitioning and their applications to material science 02.06.2013 Les Diableret, Switzerland Rezende dos Santos Leonardo Humberto; Macchi Piero;
ChemMatCARS Synchrotron Charge Density School Talk given at a conference Evaluation of electrostatic properties from the pseudoatom model 09.03.2013 Chicago, United States of America Macchi Piero;
6th Eusopean Charge Density Meeting Talk given at a conference Optical and mechanical properties of organic and organometallic materials from accurate electron density distribution 09.09.2012 High Tartras (Slovak Republik), Slovenia Macchi Piero; Chimpri Abita Shyorotra; Rezende dos Santos Leonardo Humberto;


Self-organised

Title Date Place
Gordon Conference on electron Distribution and chemical bonding 02.06.2013 Les Diablerets (Switzerland), Switzerland
CUSO course "Hydrogen Bond" 20.08.2012 Villars, Switzerland

Knowledge transfer events

Active participation

Title Type of contribution Date Place Persons involved
Presentation of the book "Modern Charge Density Analysis" Performances, exhibitions (e.g. for education institutions) 09.11.2012 radio - interview, Great Britain and Northern Ireland Macchi Piero;


Communication with the public

Communication Title Media Place Year
Talks/events/exhibitions Chemie am Samstag German-speaking Switzerland 2013

Associated projects

Number Title Start Funding scheme
160157 Physical and chemical properties from the electron density distribution of materials 01.04.2015 Project funding (Div. I-III)
125313 Properties of metal-organic materials from accurate electron density determination 01.04.2009 Project funding (Div. I-III)

Abstract

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.
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