Giovanni Salassa

A DFT Study on the Mechanism of the Cycloaddition Reaction of CO2 to Epoxides Catalyzed by Zn(Salphen) Complexes

The reaction mechanism for the Zn(salphen)/NBu4X (X = Br, I) mediated cycloaddition of CO2 to a series of epoxides, affording five-membered cyclic carbonate products has been investigated in detail by using DFT methods. The ring-opening step of the process was examined and the preference for opening at the methylene (Cβ) or methine carbon (Cα) was established. Furthermore, calculations were performed to clarify the reasons for the lethargic behavior of internal epoxides in the presence of the binary catalyst. Also, the CO2 insertion and the ring-closing steps have been explored for six differently substituted epoxides and proved to be significantly more challenging compared with the ring-opening step. The computational findings should allow the design and application of more efficient catalysts for organic carbonate formation.

Mechanism of Ligand Photodissociation in Photoactivable [Ru(bpy)2L2]2+ Complexes : A Density Functional Theory Study

A series of four photodissociable Ru polypyridyl complexes of general formula [Ru(bpy)2L2](2+), where bpy = 2,2-bipyridine and L = 4-aminopyridine (1), pyridine (2), butylamine (3), and gamma-aminobutyric acid (4), was studied by density functional theory (DFT) and time-dependent density functional theory (TDDFT). DFT calculations (B3LYP/LanL2DZ) were able to predict and elucidate singlet and triplet excited-state properties of 1-4 and describe the photodissociation mechanism of one monodentate ligand. All derivatives display a Ru --> bpy metal-to-ligand charge transfer (MLCT) absorption band in the visible spectrum and a corresponding emitting triplet (3)MLCT state (Ru --> bpy). 1-4 have three singlet metal-centered (MC) states 0.4 eV above the major (1)MLCT states. The energy gap between the MC states and lower-energy MLCT states is significantly diminished by intersystem crossing and consequent triplet formation. Relaxed potential energy surface scans along the Ru-L stretching coordinate were performed on singlet and triplet excited states for all derivatives employing DFT and TDDFT. Excited-state evolution along the reaction coordinate allowed identification and characterization of the triplet state responsible for the photodissociation process in 1-4; moreover, calculation showed that no singlet state is able to cause dissociation of monodentate ligands. Two antibonding MC orbitals contribute to the (3)MC state responsible for the release of one of the two monodentate ligands in each complex. Comparison of theoretical triplet excited-state energy diagrams from TDDFT and unrestricted Kohn-Sham data reveals the experimental photodissociation yields as well as other structural and spectroscopic features.

Extremely Strong Self-Assembly of a Bimetallic Salen Complex Visualized at the Single-Molecule Level

A bis-Zn(salphen) structure shows extremely strong self-assembly both in solution as well as at the solid-liquid interface as evidenced by scanning tunneling microscopy, competitive UV-vis and fluorescence titrations, dynamic light scattering, and transmission electron microscopy. Density functional theory analysis on the Zn(2) complex rationalizes the very high stability of the self-assembled structures provoked by unusual oligomeric (Zn-O)(n) coordination motifs within the assembly. This coordination mode is strikingly different when compared with mononuclear Zn(salphen) analogues that form dimeric structures having a typical Zn(2)O(2) central unit. The high stability of the multinuclear structure therefore holds great promise for the development of stable self-assembled monolayers with potential for new opto-electronic materials.

Ligand-Selective Photodissociation from [Ru(bpy)(4AP)4]2+ : a Spectroscopic and Computational Study

The new complex [Ru(bpy)(4AP)(4)](2+) (1), where bpy = 2,2-bipyridine and 4AP = 4-aminopyridine, undergoes selective photodissociation of two 4APs upon light excitation of the metal-ligand-to-ligand charge-transfer (MLLCT) band at 510 nm. The photoproducts of the reaction are mer-[Ru(bpy)(4AP)(3)(H(2)O)](2+) (2a) and trans-(4AP)[Ru(bpy)(4AP)(2)(H(2)O)(2)](2+) (3a). Photodissociation occurs in two consecutive steps with quantum yields of phi(1) = (6.1 +/- 1.0) x 10(-3) and phi(2) = (1.7 +/- 0.1) x 10(-4), respectively. Complex 1 was characterized by combined spectroscopic and theoretical techniques. EXAFS experiments at the Ru K-edge (22 117 eV) of 1 in an aqueous solution gave a Ru-N distance of 2.09 +/- 0.01 A. Photoproducts were characterized by electronic spectroscopy, 1D and 2D NMR, and mass spectrometry. Singlet and triplet excited states of 1 were studied by density functional theory (DFT) and time-dependent DFT for characterizing the optical properties of the complex. In the singlet state, (1)MC (metal-centered) dissociative states lie 0.65 eV above the main (1)MLLCT transition in the visible region of the UV-vis absorption spectrum. In the triplet state, the energy difference between these states is not reduced. However, potential energy curves of singlet and triplet excited states of 1 along the Ru-N(axial 4AP) and Ru-N(equatorial 4AP) stretching coordinates show that the release of the first 4AP may occur from the triplet state by mixing of (3)MLLCT and (3)MC dissociative states. This mixing is favored when the Ru-N(equatorial 4AP) bond is elongated, explaining the formation of the photoproduct 2a.

Versatile Switching in Substrate Topicity: Supramolecular Chirality Induction in Di‐ and Trinuclear Host Complexes

Supramolecular chirality effects have been achieved both for ditopic and monotopic substrates by using a programmable bis-salphen scaffold that incorporates either two or three Zn nuclei. The dinuclear host shows preferential chirogenesis in the presence of ditopic systems, whereas effective chirality transfer to the trinuclear complex is realized through monotopic binding. The mode of binding in the trinuclear host has been investigated through X-ray crystallography, CD measurements, UV/Vis spectroscopy, and DFT analysis. The bis-salphen scaffold holds promise for the development of substrate-specific host systems useful for determination of the absolute configuration of various types of organic molecules.

A Short Desymmetrization Protocol for the Coordination Environment in Bis-salphen Scaffolds

A remarkable short preparation of desymmetrized bis-salphen scaffolds is presented. The protocol consists of an hydroxide-mediated hydrolysis of Lewis acidic bis-Zn(salphen) complexes yielding C(s)-symmetric diimine/amine salts that can be selectively transformed into bis-salphens with dissymmetric substitution patterns within each salphen unit under mild conditions. These isolated nonsymmetrical bis-salphen derivatives do not show signs of imine scrambling or decomposition due to a metal template effect. A possible rationale is provided for the formation and isolation of one of the intermediate bis-phenolate salts, and the hypothesis involves H-bond directed hydrolysis of the nearest located imine bond across the bis-salphen scaffold.

Turning Supramolecular Receptors into Chemosensors by Nanoparticle-Assisted “NMR Chemosensing”

By exploiting a magnetization transfer between monolayer-protected nanoparticles and interacting analytes, the NMR chemosensing protocol provides a general approach to convert supramolecular receptors into chemosensors via their conjugation with nanoparticles. In this context, the nanoparticles provide the supramolecular receptor not only with the bulkiness necessary for the NMR chemosensing approach but also with a different selectivity as compared to the parent receptor. We here demonstrate that gold nanoparticles of 1.8 nm core coated with a monolayer of 18-crown-6 ether derivatives can detect and identify protonated primary amines in methanol and in water, and even discriminate between two biogenic diamines that are selectively detected over monoamines and α-amino acids.

Structure of [Ru(bpy)n(AP)(6-2n)]2+ homogeneous complexes: DFT calculation vs. EXAFS

We used EXAFS and DFT calculations to investigate the structure of [Ru(bpy)(AP)4]2+ and [Ru(bpy)2(AP)2]2+ (bpy=2-2-bipyridyne, AP=4-aminopyridyne) in aqueous solution (10 mM). These derivatives are of potential interest since, upon direct irradiation, they can form reactive aqua-species able to bind to macromolecules. An attempt has been made to determine with EXAFS the structure of the photodissociation product of the [Ru(bpy)2(AP)2]2+ complex, where a water molecule fill the coordination vacancy left by an AP ligand resulting in [Ru(bpy)2(AP)(H2O)]2+. Unfortunately, co-presence in the experimental sample of both original and photodissociated complexes, causes the failure of the analysis. This failure was due to the structural complexity of both systems and to the similarity in their EXAFS signals. This work underlines the potentialities and the limits of EXAFS spectroscopy when dealing with highly diluted samples where the local environment of the adsorbing atom is characterized by structured ligands: the local environment of Ru is correctly reproduced when dealing with homogeneous samples, while the co-presence of two or more different species makes the data analysis highly critical.

Supramolecular bulky phosphines comprising 1,3,5-triaza-7-phosphaadamantane and Zn(salphen)s: structural features and application in hydrosilylation catalysis

The use of the commercially available, bifunctional phosphine 1,3,5-triaza-7-phosphaadamantane (abbreviated as PN3) in conjunction with a series of Zn(salphen) complexes leads to sterically encumbered phosphine ligands as a result of (reversible) coordinative Zn-N interactions. The solid state and solution phase behaviour of these supramolecular ligand systems have been investigated in detail and revealed their stoichiometries in the solid state observed by X-ray crystallography, and those determined in solution by NMR and UV-Vis spectroscopy. Also, upon application of these supramolecular bulky phosphines in hydrosilylation catalysis employing 1-hexene as a substrate, the catalysis data infer the presence of an active Rh species with two coordinated, bulky PN3/Zn(salphen) assembly units having a maximum of three Zn(salphen)s associated per PN3 scaffold, with an excess of bulky phosphines hardly affecting the overall activity.