Jean-Pierre Brog

Polymorphism, what it is and how to identify it: a systematic review

This review on polymorphism is a personal, non-comprehensive view on the field of polymorphism – a term which is often misused. Indeed, the discussion about polymorphism and related terms is still ongoing in the area of crystal engineering. This is why we felt it timely to look into the historical development of its definition and to delimit it. A short introduction to thermodynamic aspects and characterization methods of polymorphs is given. One chapter is then dedicated to polymorphism of elements and inorganic compounds, before discussing the term for organic and organo-metallic compounds. Chosen examples are given each time to illustrate the cases of polymorphism. In the end, the conclusion yields three flow schemes useful in determining polymorphism for each compound class.

Nanomaterials Meet Li-ion Batteries.

Li-ion batteries are used in many applications in everyday life: cell phones, laser pointers, laptops, cordless drillers or saws, bikes and even cars. Yet, there is room for improvement in order to make the batteries smaller and last longer. The Fromm group contributes to this research focusing mainly on nanoscale lithium ion cathode materials. This contribution gives an overview over our current activities in the field of batteries. After an introduction on the nano-materials of LiCoO(2) and LiMnPO(4), the studies of our cathode composition and preparation will be presented.

Density functional theory study of the multimode Jahn-Teller effect – ground state distortion of benzene cation

The multideterminental-DFT approach performed to analyze Jahn-Teller (JT) active molecules is described. Extension of this method for the analysis of the adiabatic potential energy surfaces and the multimode JT effect is presented. Conceptually a simple model, based on the analogy between the JT distortion and reaction coordinates gives further information about microscopic origin of the JT effect. Within the harmonic approximation the JT distortion can be expressed as a linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation, which allows calculating the Intrinsic Distortion Path, IDP, exactly from the high symmetry nuclear configuration to the low symmetry energy minimum. It is possible to quantify the contribution of different normal modes to the distortion, their energy contribution to the total stabilization energy and how their contribution changes along the IDP. It is noteworthy that the results obtained by both multideterminental-DFT and IDP methods for different classes of JT active molecules are consistent and in agreement with available theoretical and experimental values. As an example, detailed description of the ground state distortion of benzene cation is given.

Early-Stage Sustainability Evaluation of Nanoscale Cathode Materials for Lithium Ion Batteries

Results of an early-stage sustainability evaluation of two development strategies for new nanoscale cathode materials for Li-ion batteries are reported: (i) a new production pathway for an existing material (LiCoO2 ) and (ii) a new nanomaterial (LiMnPO4 ). Nano-LiCoO2 was synthesized by a single-source precursor route at a low temperature with a short reaction time, which results in a smaller grain size and, thereby, a better diffusivity for Li ions. Nano-LiMnPO4 was synthesized by a wet chemical method. The sustainability potential of these materials was then investigated (at the laboratory and pilot production scales). The results show that the environmental impact of nano-LiMnPO4 is lower than that of the other examined nanomaterial by several factors regardless of the indicator used for comparison. In contrast to commercial cathode materials, this new material shows, particularly on an energy and capacity basis, results of the same order of magnitude as those of lithium manganese oxide (LiMn2 O4 ) and only slightly higher values than those for lithium iron phosphate (LiFePO4 ); values that are clearly lower than those for high-temperature LiCoO2 .

Mixed metal multinuclear Cr(III) cage compounds and coordination polymers based on unsubstituted phenolate: design, synthesis, mechanism, and properties

The use of alkali aryloxide reagents in organo-metallic synthesis often depends on their solubility, a property derived from their structure. The regain of interest of alkali aryloxides also originates from the discovery of high-temperature superconducting compounds, which has generated a great interest in the formation of oxide materials and other ceramics. Thus, many alkoxides of yttrium and copper are common precursors for oxide materials. Moreover, the synthesis of heterobimetallic alkoxides has provided a facile route for obtaining soluble, volatile, and generally monomeric species. These heterobimetallic complexes can thus serve as valuable precursors for making mixed metal oxides. This is however not the only possible application for this type of compounds. These complexes can be used as starting compounds for the syntheses of more complex structures. In this work, the salt elimination and ligand exchange reaction of chromium(II) chloride with lithium phenoxide yields a mixed metal lithium-chromium(II) phenoxide. Using this latter as intermediately formed starting material and combining the substitution reaction with an oxidation process, we have gained access to new polynuclear chromium(III) aryloxide complexes. While a 1D coordination polymer based on chromium(III) is obtained in a first reaction by serendipity, the controlled addition of water to the Cr(II) complex leads to three new discrete chromium(III) cluster compounds. The use of deuterated species allowed to confirm the oxidation based on the addition of water by detection of H2, HD and D2. During these investigations, we have also identified a THF-adduct of chromium(II) chloride, used in the literature as precursor in numerous syntheses, but with a hitherto unknown structure. A. Crochet, J-P. Brog, and K. M. Fromm, Cryst. Growth Des., 2016, 16 (1), pp 189–199.

Cr(II) complex: water reductant and starting compound for new Cr(III) compounds

The use of alkali aryloxide reagents in organo-metallic synthesis often depends on their solubility, a property derived from their structure. The regain of interest of alkali aryloxides also originates from the discovery of high-temperature superconducting compounds, which has generated a great interest in the formation of oxide materials and other ceramics. Thus, many alkoxides of yttrium and copper are common precursors for oxide materials. Moreover, the synthesis of heterobimetallic alkoxides has provided a facile route for obtaining soluble, volatile, and generally monomeric species. These heterobimetallic complexes can thus serve as valuable precursors for making metal oxides but it is not the only possible application for this type of compounds. These complexes can be used as starting compounds for syntheses of more complex structures. In this work, the salt elimination and ligand exchange reaction of chromium(II) chloride with lithium phenoxide yields a mixed metal lithium-chromium(II) phenoxide. Using this latter as intermediately formed starting material and combining the substitution reaction with an oxidation process, we have gained access to new polynuclear chromium(III) aryloxide complexes. While a 1D coordination polymer based on chromium(III) is obtained in a first reaction by serendipity, the controlled addition of water to the Cr(II) complex leads to three new discrete chromium(III) cluster compounds. The use of deuterated species allowed to confirm the oxidation based on the addition of water by detection of H2, HD and D2. During these investigations, we have also identified a THF-adduct of chromium(II) chloride, used in the literature as precursor in numerous syntheses, but with a hitherto unknown structure. Figure 1: Oxidation of a Cr(II) complex by water and formation of a new Cr(III) complex.

Polymorphism, what it is and how to identify it.

Polymorphism is a very important phenomenon not only in basic research, but certainly in pharmaceutical industry and materials science. Polymorphs possess different properties, for instance the solubility or the mechanical resistance can differ dramatically from one polymorph to the other – properties which can be crucial for their application. Hence, it is important to be able to control the formation of polymorphs and to understand their formation. We here gave some insights into the basic knowledge of polymorph formation and their identification and characterization in order to give an overview on the current state of the art. In order to give interested peoples a tool in hand to test their compounds for polymorphism, we established a series of flow sheets to follow, depending on the class of compounds, hoping that they are useful for many scientists who are not so well acquainted with polymorphism. The presented schemes resume thus the identification steps for polymorphs. It should also help to use the term polymorph correctly in order to reduce the number of publications in which this term is not used in a correct way.