Groupe de recherche Reber : Département de chimie, Université de Montréal

Ce rapport présente les membres du groupe de 1991 à 2023

Metal-ligand bonding in six-coordinate d-block complexes probed by luminescence spectroscopy at variable pressure

Luminescence spectra measured at variable pressure can reveal unique insight on ground- and emitting state properties of transition metal compounds. This chapter summarizes illustrative results for chromium(III) complexes with the d3 electron configuration and oxo complexes of rhenium(V) and molybdenum(IV) with the d2 configuration. Their luminescence transitions only involve electronic configuration changes within the t2 (O point group) molecular orbitals, leading to narrow spin-flip bands and broad bands with vibronic structure for the chromium(III) and metal-oxo complexes, respectively

On the spectrum of hypergraphs

Here we study the spectral properties of an underlying weighted graph of a non-uniform hypergraph by introducing different connectivity matrices, such as adjacency, Laplacian and normalized Laplacian matrices. We show that different structural properties of a hypergrpah, can be well studied using spectral properties of these matrices. Connectivity of a hypergraph is also investigated by the eigenvalues of these operators. Spectral radii of the same are bounded by the degrees of a hypergraph. The diameter of a hypergraph is also bounded by the eigenvalues of its connectivity matrices. We characterize different properties of a regular hypergraph characterized by the spectrum. Strong (vertex) chromatic number of a hypergraph is bounded by the eigenvalues. Cheeger constant on a hypergraph is defined and we show that it can be bounded by the smallest nontrivial eigenvalues of Laplacian matrix and normalized Laplacian matrix, respectively, of a connected hypergraph. We also show an approach to study random walk on a (non-uniform) hypergraph that can be performed by analyzing the spectrum of transition probability operator which is defined on that hypergraph. Ricci curvature on hypergraphs is introduced in two different ways. We show that if the Laplace operator, $\Delta$, on a hypergraph satisfies a curvature-dimension type inequality $CD (\mathbf{m}, \mathbf{K})$ with $\mathbf{m}>1$ and $\mathbf{K}>0$ then any non-zero eigenvalue of $- \Delta$ can be bounded below by $\frac{ \mathbf{m} \mathbf{K}}{ \mathbf{m} -1 }$. Eigenvalues of a normalized Laplacian operator defined on a connected hypergraph can be bounded by the Ollivier's Ricci curvature of the hypergraph

Bulk or surface grafted silylated Ru(ii) complexes on silica as luminescent nanomaterials

A series of Ru(II) complexes with monosilylated-dipyridine ligand have been synthesized and fully characterized and were then covalently attached to silica nanoparticles. Two types of hybrids were obtained depending on the experimental procedure. In the first approach, metal complexes were incorporated inside the silica nanoparticles leaving a free hydroxylated silica surface for further functionalization. These silica based nanohybrids are similar to the well known nanoparticles encapsulating [Ru(bpy)3]2+ complexes preventing the release of the dye when used in aqueous or organic solutions. Size and luminescence properties vary throughout the series of metal complexes. The second approach leads to ruthenium(II) complexes covalently attached to the silica nanoparticle surface via hydrolysis and condensation of the ethoxysilyl group with silanol sites of Ludox type silica nanoparticles. This leads to the grafting of a monolayer for complexes with the monoethoxysilyl dipyridine ligand. In contrast, the complexes with triethoxysilyl ligands can lead to small amounts of oligomers, but their quantity is limited by the sterical constraints imposed by the molecular structure. The size of the hybrids depends on the starting particles. 29Si and 13C solid state NMR are used to characterize silica surface properties whereas TEM and SEM confirm nanosize and morphology of the hybrids. The complexes and the nanohybrids are luminescent, with variations for ruthenium(II) complexes that are covalently incorporated or grafted on the silica surfac

Gene Expression during Survival of Escherichia coli O157:H7 in Soil and Water

The in vitro survival of Escherichia coli O157:H7 at 15°C under two experimental conditions (sterile soil and sterile natural water) was examined. DNA microarrays of the entire set of E. coli O157:H7 genes were used to measure the genomic expression patterns after 14 days. Although the populations declined, some E. coli O157:H7 cells survived in sterile stream water up to 234 days and in sterile soil for up to 179 days. Cells incubated in soil microcosms for 14 days expressed genes for antibiotic resistance, biosynthesis, DNA replication and modification, metabolism, phages, transposons, plasmids, pathogenesis and virulence, antibiotic resistance, ribosomal proteins, the stress response, transcription, translation, and transport and binding proteins at significantly higher levels than cells grown in Luria broth. These results suggest that E. coli O157:H7 may develop a different phenotype during transport through the environment. Furthermore, this pathogen may become more resistant to antibiotics making subsequent infections more difficult to treat

Unconventional field induced phases in a quantum magnet formed by free radical tetramers

We report experimental and theoretical studies on the magnetic and thermodynamic properties of NIT-2Py, a free radical-based organic magnet. From magnetization and specific heat measurements we establish the temperature versus magnetic field phase diagram which includes two Bose-Einstein condensates (BEC) and an infrequent half magnetization plateau. Calculations based on density functional theory demonstrates that magnetically this system can be mapped to a quasi-two-dimensional structure of weakly coupled tetramers. Density matrix renormalization group calculations show the unusual characteristics of the BECs where the spins forming the low-field condensate are different than those participating in the high-field one.Comment: 12 pages, 12 figure

LGM glaciations in the northeastern Anatolian mountains: New insights

Barhal Valley belongs to the Çoruh Valley System in the Kaçkar Mountains of northeastern Anatolia. This 13 km long valley is located to the south of the main weather divide and to the east of Mt. Kaçkar, with the highest peak of the mountain range being 3932 m. Today, source of an average yearly precipitation of 2000 mm of moisture is the Black Sea, situated approximately 40 km to the north of the study site. Glaciers of the Last Glacial Maximum (LGM) descended directly from Mt. Kaçkar and reached an altitude of ca. 1850 m a.s.l. (above sea level). In this study, we are exploring whether the position of Barhal Valley to the south of the main weather divide and its east–west orientation have an influence on the existence and expansion of paleoglaciers. Here, we present 32 new cosmogenic 36Cl dates on erratic boulders from the Çoruh Valley System. We reconstructed three geomorphologically well-contained glacier advances in the Barhal Valley, namely at 34.0 ± 2.3 ka, 22.2 ± 2.6 ka, and 18.3 ± 1.7 ka within the time window of the global LGM. Field evidence shows that the glacier of the 18.3 ± 1.7 ka advance disappeared rapidly and that by the latest time, at 15.6 ± 1.8 ka, the upper cirques were ice-free. No evidence for Lateglacial glacier fluctuations was found, and the Neoglacial activity is restricted to the cirques with rock glaciers. A range of 2700 to 3000 m for the Equilibrium Line Altitude (ELA) at the LGM was reported based on modeling of the glacial morphology. We determined that the most likely position of the LGM ELA in the Çoruh Valley System was at 2900 m a.s.l. We suggest an alternative moisture source to the direct transport from the Black Sea for the ice accumulation in the Eastern Black See Mountains. The shift of the Polar Front and of the Siberian High Pressure System to the south during the LGM resulted in the domination of easterly airflow to the Caucasus and Kaçkar Mountains with moisture from expanded lakes in central–western Siberia and from the enlarged Aral- and Caspian Seas