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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 125313
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 01.04.2009 - 31.03.2012
Approved amount 192'609.00
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Lay Summary (English)

Lead
Lay summary

The electron density is the fundamental property of matter. The behavior of a material is strictly connected with the way in which electrons are distributed and move. Very accurate determinations of the electron density distribution are now possible, even in complex molecules or solids containing heavy metal atoms and therefore many electrons. Both theoretical (mainly, ab initio molecular orbital calculations) and experimental (X-ray diffraction) techniques serve this purpose and are often complementary. The analysis of chemical bonding is the first step to predict the behavior of a material. This is particularly cogent when a mixed character bonding is present, as it often occurs in organometallic species.  

More recently, many theoretical progresses were made to use electron density distribution also for interpretation and quantification of intermolecular interactions. These studies found many applications in biomolecular chemistry, whereas less attention was paid so far to metal-organic coordination polymers. These species are very interesting because they can produce multi-dimensional infinite networks able to host, select and organize guest molecules carrying specific properties sometime combined with the framework electronic, optic or magnetic behavior. In this field, the accurate electron density distribution is fundamental to understand, for example, the interaction between the framework and the guest (therefore predicting the most efficient supramolecular organization) or to predict the actual property of the material. 

This project aims to use the huge potentiality of electron density analysis for interpretation of chemical bonding and supramolecular assembly as well as for prediction of properties in metal-organic molecular materials. X-ray single crystal diffraction, theoretical ab initio or semi empirical calculations will be used in combination.

Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
A guided tour through modern charge density analysis
Gatti Carlo, Macchi Piero (2012), A guided tour through modern charge density analysis, in Macchi Piero, Gatti Carlo (ed.), Springer, Berlin, 1.
Bond Orders in Metal-Metal Interactions Through Electron Density Analysis
Farrugia LJ, Macchi P (2012), Bond Orders in Metal-Metal Interactions Through Electron Density Analysis, in Structure and Bonding, 146, 127-158.
Cryo-crystallography. Diffraction at low temperature and more
Macchi Piero (2012), Cryo-crystallography. Diffraction at low temperature and more, in Topics in Current Chemistry, 33-68.
Low-energy contamination of Mo microsource X-ray radiation: analysis and solution of the problem
Macchi P, Burgi HB, Chimpri AS, Hauser J, Gal Z (2011), Low-energy contamination of Mo microsource X-ray radiation: analysis and solution of the problem, in JOURNAL OF APPLIED CRYSTALLOGRAPHY, 44, 763-771.
Modern Charge Density Analysis
Gatti Carlo, Macchi Piero (2011), Modern Charge Density Analysis, Springer, Dordrecht.
Restoring orbital thinking from real space descriptions: bonding in classical and non-classical transition metal carbonyls
Tiana D, Francisco E, Blanco MA, Macchi P, Sironi A, Pendas AM (2011), Restoring orbital thinking from real space descriptions: bonding in classical and non-classical transition metal carbonyls, in PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 13(11), 5068-5077.
Bonding in Classical and Nonclassical Transition Metal Carbonyls: The Interacting Quantum Atoms Perspective
Tiana D, Francisco E, Blanco MA, Macchi P, Sironi A, Pendas AM (2010), Bonding in Classical and Nonclassical Transition Metal Carbonyls: The Interacting Quantum Atoms Perspective, in JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 6(4), 1064-1074.
Four tetrairidium carbonyl clusters linked by six diphosphino ligands: synthesis and X-ray structure of [{Ir-4(CO)(9)}(4)(dppmb)(6)] (dppmb=1,4-bis(diphenylphosphinomethyl)benzene
Peli G, Daghetta M, Macchi P, Sironi A, Garlaschelli L (2010), Four tetrairidium carbonyl clusters linked by six diphosphino ligands: synthesis and X-ray structure of [{Ir-4(CO)(9)}(4)(dppmb)(6)] (dppmb=1,4-bis(diphenylphosphinomethyl)benzene, in DALTON TRANSACTIONS, 39(5), 1188-1190.
Slow Relaxation of the Magnetization in Non-Linear Optical Active Layered Mixed Metal Oxalate Chains
Cariati E, Ugo R, Santoro G, Tordin E, Sorace L, Caneschi A, Sironi A, Macchi P, Casati N (2010), Slow Relaxation of the Magnetization in Non-Linear Optical Active Layered Mixed Metal Oxalate Chains, in INORGANIC CHEMISTRY, 49(23), 10894-10901.
Stabilization through p-dimethylaminobenzaldehyde of a new NLO-active phase of [E-4-(4-dimethylaminostyryl)-1-methylpyridinium] iodide: synthesis, structural characterization and theoretical investigation of its electronic properties
Nunzi F, Fantacci S, Cariati E, Tordin E, Casati N, Macchi P (2010), Stabilization through p-dimethylaminobenzaldehyde of a new NLO-active phase of [E-4-(4-dimethylaminostyryl)-1-methylpyridinium] iodide: synthesis, structural characterization and theoretical investigation of its electronic properties, in JOURNAL OF MATERIALS CHEMISTRY, 20(36), 7652-7660.
On the Interpretation of the Source Function
Farrugia LJ, Macchi P (2009), On the Interpretation of the Source Function, in JOURNAL OF PHYSICAL CHEMISTRY A, 113(37), 10058-10067.
Resonance Structures and Electron Density Analysis
Macchi P (2009), Resonance Structures and Electron Density Analysis, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48(32), 5793-5795.

Collaboration

Group / person Country
Types of collaboration
University fo Glasgow Great Britain and Northern Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
University of Oviedo Spain (Europe)
- in-depth/constructive exchanges on approaches, methods or results

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
IUCr Internation School on Charge Density Talk given at a conference XD2006 tutorial 30.08.2011 Jaca, Spain Macchi Piero; Kawczuk-Pantula Anna; Chimpri Abita Shyorotra;
XXII IUCr General Assembly Poster Atomic polarizabilities and multipolar model 22.08.2011 Madrid, Spain Macchi Piero; Kawczuk-Pantula Anna;
Meeting of the American Crystallographic Association Talk given at a conference Properties of Molecular Materials from Electron Density distribution 31.05.2011 New Orleans (USA), United States of America Macchi Piero; Kawczuk-Pantula Anna;


Self-organised

Title Date Place
Swiss Crystallographic Meeting 2011 16.09.2011 Bern, Switzerland
Gordon Research Conference on "Electron Distribution and Chemical Bonding" 12.06.2010 Mount Holyooke, United States of America
Schhool on Scattering Techniques: From Microscopic To Atomic Structures 30.08.2009 Camerino (Italy), Italy

Associated projects

Number Title Start Funding scheme
141271 Properties of metal-organic materials from accurate electron density determination 01.04.2012 Project funding (Div. I-III)
128724 Purchase of a single crystal X-ray diffractometer for high resolution and accurate studies on molecular crystals 01.12.2009 R'EQUIP

Abstract

Knowing the electron density distribution is fundamental for all chemistry. Chemical reactions, molecular properties as well as supramolecular assembly and material properties all depend on the distribution of electrons in the compound and, more specifically, in the chemical bonds or in the non-bonding regions.Progresses in the last decades allow nowadays very accurate determinations of the electron density distribution, even in molecules or solids containing heavy metal atoms and therefore many electrons. Both theoretical (mainly, ab initio molecular orbital calculations) and experimental (X-ray diffraction) techniques serve this purpose and are often complementary. The analysis of chemical bonding is a very important starting point to predict the behavior of a material. This is particularly relevant when a mixed character bonding is present, as often occurs in organometallic species. Indeed, much debate is still open on the nature of unusual ag-gregation between organic ligands and metal centers. For example, the degree of covalency, the peculiar genealogy of the chemical bonds to a transition metal and the degree of electron delocalization are usually matter of study and the electron density analysis has often solved the controversies. More recently, many theoretical progresses were made to use electron density distribution also for interpretation and quantification of intermolecular interactions. These studies found many applications in biomolecular chemistry, whereas less attention was paid so far to metal-organic coordination polymers. These species are very interesting because they can produce multidi-mensional infinite networks able to host, select and organize guest molecules carrying specific properties sometime combined with the framework electronic, optic or magnetic behavior. In this field, the accurate electron density distribution is fundamental to understand, for example, the interaction between the framework and the guest (therefore predicting the most efficient supramolecular organization) or to predict the actual property of the material. This project aims to use the huge potentiality of electron density analysis for interpretation of chemical bonding and supramolecular assembly as well as for prediction of properties in metal-organic molecular materials. X-ray single crystal diffraction, theoretical ab initio or semi empirical calculations will be used in combination.
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