Project

Back to overview

Chemical bonding and reactions in molecular crystals at high pressure

Applicant Macchi Piero
Number 144534
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 01.10.2012 - 30.09.2015
Approved amount 311'482.00
Show all

Keywords (7)

solid state chemistry; crystallography; density functional theory; chemical bonding; X-ray diffraction; high pressure; polymorphism

Lay Summary (English)

Lead
Pressure is an energy density. When a material is compressed, it rises its energy, which is a way to induce structural transformations. The higher the pressure, the more sever can be the transforamtions, ranging from simple crystal packing modifications and conformational rearrangements of a molecule to stretching/compression of some strong chemical bond and solid state chemical reactions. In this project we investigate some representative example of each kind of transformation. In particualr, we analyse conformational rearrangements in organometallic molecules, breathing effect in metal-organic frameoworks, pressure induced changes of the Jahn Teller distortions in magnetic coordination polymers and chemical reactions in organic crystals (in particular nucleophilic additions).
Lay summary

The goal of this project is that of using pressure as a medium to induce structural modifications in crystalline phases of organic and metal organic molecules or polymers, with the intent to discover new forms of the materials, potentially with new properties.

In this study, we have so far characterized the transformation occurring in metal carbonyl dimers under pressure, in particular clarifying the stereochemistry of the high pressure form of Mn2(CO)10, which was still matter of debate, lacking of X-ray diffraction analysis.

Moreover, we have investigated several coordination polymers. Some of them are magnetically active, due to the presence of a magnetic metal ion. In particular we have studied the [CuF2(H2O)2](pyrazine)x (x=1,2) system, known to undergo sequential orbital ordering as a function of pressure. We have discovered one new high pressure phase and an ambient phase of new stoichiometry. The kinetics of these transformation is investigated, with a new high pressure technique (results will be submitted for publication soon).

Other coordination polymers are metal organic frameworks based on benzotriazole-5-carboxylate as anionic linker and Zn, Co, Mn as metal connectors. These MOF are flexible enough to show the so-called breathing effect, i.e. contraction expansion of the pores due to desorption or adsorption of (small) guest molecules. we found new interesting phases, pressure or temperature induced, that demonstrate the occurrence of coordination by the guest molecules. These results are going to be submitted for publication.

Th most appealing results of our study are the functionalization of some organic molecules (dicarboxylic acids and aromatic annulenes) that bring to pre-reactive states and eventually to pressure induced polymerization, all step characterized by synchrotron X-ray diffraction.

Direct link to Lay Summary Last update: 19.12.2014

Responsible applicant and co-applicants

Employees

Publications

Publication
Anagostic Interactions under Pressure: Attractive or Repulsive?
Scherer W., Dunbar A. C., Barquera-Lozada J. E., Schmitz D., Eickerling G., Kratzert D., Stalke D., Lanza A., Macchi P., Casati N., Ebad-Allah J., Kuntscher C. (2015), Anagostic Interactions under Pressure: Attractive or Repulsive?, in Angew. Chem., 54, 2505-2509.
Back to 1D Detectors: Benefits for High-Pressure Powder X-ray Diffraction
Fisch Martin, Lanza Arianna, Macchi Piero, Casati Nicola (2015), Back to 1D Detectors: Benefits for High-Pressure Powder X-ray Diffraction, in Journal of Applied Crystallography, 48, 1956-1963.
Kinetic Control of High-Pressure Solid-State Phase Transitions: A Case Study on L-Serine
Fisch Martin, Lanza Arianna, Boldyreva Elena, Macchi Piero, Casati Nicola (2015), Kinetic Control of High-Pressure Solid-State Phase Transitions: A Case Study on L-Serine, in Journal of Physical Chemistry C, 119, 18611-18617.
Pressure-induced oversaturation and phase transition in zeolitic imidazolate frameworks with remarkable mechanical stability
Zhao Pu, Bennet Thomas, Casati Nicola, Lampronti Giulio, Moggach Stephen, Redfern Simon (2015), Pressure-induced oversaturation and phase transition in zeolitic imidazolate frameworks with remarkable mechanical stability, in Dalton Transactions, 44, 4498-4503.
Solid-state reversible nucleophilic addition in a highly flexible MOF
Lanza Arianna, Germann Luzia, Fisch Martin, Casati Nicola, Macchi Piero (2015), Solid-state reversible nucleophilic addition in a highly flexible MOF, in Journal of the American Chemical Society, 137, 13072-13078.
"Off-axis" metal-metal bond in Mn2(CO)10 at high pressure
Macchi Piero, Casati Nicola, Evans Shaun Russell, Gozzo Fabia, Simoncic Petra, Tiana Davide (2014), "Off-axis" metal-metal bond in Mn2(CO)10 at high pressure, in Chemical Communiation, 50, 12824 - 128247.
Chemical reactivity at high pressure: the ordered polymerization of oxalic acid
Casati Nicola, Jephcoat Andrew, Wilhelm Heribert, Macchi Piero (2014), Chemical reactivity at high pressure: the ordered polymerization of oxalic acid, in Acta Crystallographica Sect. A, 70, C898.
Electron density of molecular crystals at high pressure from synchrotron data
Macchi Piero, Casati Nicola, Kleppe Annette, Jephcoat. Andrew (2014), Electron density of molecular crystals at high pressure from synchrotron data, in Acta Crystallographica Sect. A, 70, C1340.
New Magnetic Frameworks of [(CuF2(H2O)2)x(pyz)]
Lanza Arianna, Fiolka Christophe, Fisch Martin, Casati Nicola, Skoulatos Markos, Ruegg Christian, Krämer Karl, Macchi Piero (2014), New Magnetic Frameworks of [(CuF2(H2O)2)x(pyz)], in Chemical Communication, 50, 14504-14507.
Modular structure of a robust microporous MOF based on Cu 2 paddle-wheels with high CO 2 selectivity
Seco José M., Fairen-Jimenez David, Calahorro Antonio J., Mendéz-Linan Laura, Pérez-Mendoza Manuel, Casati Nicola, Colacio Enrique, Rodrıguez-Diéguez Antonio (2013), Modular structure of a robust microporous MOF based on Cu 2 paddle-wheels with high CO 2 selectivity, in Chemical Communications, 49, 11329.

Collaboration

Group / person Country
Types of collaboration
Department Chemistry University of Milan Italy (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Diamond Light Sources Great Britain and Northern Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Institute of Solid State Chemistry, University of Novosibirsk Russia (Europe)
- in-depth/constructive exchanges on approaches, methods or results
University of Oxford Great Britain and Northern Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Universit of Augsburg, Department opf Physics Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Congress of the Swiss Crystallographic Association Talk given at a conference Solid-state nucleophilic addition in a highly flexible MOF 14.09.2015 Neuchatel, Switzerland Macchi Piero; Fisch Martin; Lanza Arianna;
Congress of the Swiss Crystallographic Association Poster Back to 1D Detectors: Benefits for High - Pressure Powder X - ray Diffraction 14.09.2015 Neuchatel, Switzerland Macchi Piero; Lanza Arianna; Casati Nicola; Fisch Martin;
29th European Crystallographic Meeting Poster Solid-State nucleophilic addition reaction in a highly flexible metal organic framework (MOF) 24.08.2015 Rovinji, Croatia Macchi Piero; Fisch Martin; Casati Nicola; Lanza Arianna;
29th European Crystallographic Meeting Poster Kinetic control on High pressure solid state phase transitions 24.08.2015 Rovinji, Croatia Macchi Piero; Lanza Arianna; Casati Nicola; Fisch Martin;
XVIII Sagamore Conference Talk given at a conference Electron density in molecules under high pressure 07.06.2015 Santa Margherita di Pula, Cagliari, Italy Macchi Piero; Casati Nicola;
SILS-AIC Joint meeting Talk given at a conference ressure - induced structural and magnetic transformations in [(CuF 2 (H 2 O) 2 ) x (pyz)] polymers 15.09.2014 Firenze, Italy Casati Nicola; Macchi Piero; Lanza Arianna;
IUCr General Assembly Talk given at a conference Electron density of molecular crystals at high pressure from synchrotron data 04.08.2014 Montreal, Canada Casati Nicola; Macchi Piero;
IUCr general Assembly Talk given at a conference Chemical reactivity at high pressure: the ordered polymerization of oxalic acid 04.08.2014 Montreal, Canada Macchi Piero; Casati Nicola;


Awards

Title Year
Panalytical Award (Arianna Lanza) 2015
travel grant to attend the AIC-SILS Joint meeting and to present results of the research, issued by the Swiss Crystallographic Association 2014

Associated projects

Number Title Start Funding scheme
126788 Chemical bonding in molecular crystals at high pressure 01.10.2009 Project funding (Div. I-III)
162861 Chemical bonding and reactions in molecular crystals at high pressure 01.10.2015 Project funding (Div. I-III)

Abstract

This project is connected with a previous SNF funded project, focused on the structural characterization of organic and organometallic molecular crystals, compressed at high pressure. We investigate here intra- and inter-molecular interactions, modified by the external stress with the purpose to improve the knowledge of the chemical bonding and interactions. A central aspect of this project is the focus on a new and more ambitious aim: the characterization of pressure induced reactions, using the crystal structures at intermediate compression stages as a "tool" to visualize reaction pathways. The theoretical and experimental structural characterization of materials are used to investigate: a) the role of the most relevant intermolecular interactions (like hydrogen bonding) on the hardness of a material; b) the role of molecular and intermolecular interactions on specific electronic or optic properties of materials; c) the pressure induced nucleophilic/electrophilic reactions to polymers or oligomers.This project is carried out using crystal engineering for the preparation of the new materials, utilizing a range of investigative techniques, such as X-ray/neutron diffraction, IR and Raman spectroscopy, polarizing microscopy on single crystals and powders, compressed in high pressure cells. Moreover, theoretical calculations with density functional theory in the solid state are used to predict and rationalize the pressure induced structural transformations.The major expected outcome is the discovery and the characterization of new polymeric forms of simple organic molecules, with important implications for material science.
-