showing 13 related works from this author
New light on an old debate: does the RCN–PtCl2 bond include any back-donation? RCN←PtCl2 backbonding vs. the IR νCN blue-shift dichotomy in organoni…
2019
For a series of organonitrile [RCN (R = Me, CF3, Ph, CH3Ph, CF3Ph)] ligands, the nature of the N–Pt bond in the related cis-/trans-(RCN)2PtCl2 complexes has been computationally investigated by Density Functional Theory. A fragment based bond analysis has been performed in the canonical Kohn–Sham molecular orbitals framework, and it has been ultimately assessed that this bond is characterized both by N→Pt σ and by N←Pt π contributions. Voronoi Deformation Density charges further confirms the occurrence of N←Pt π interactions. Moreover, the Energy Decomposition Analysis-Natural Orbital for Chemical Valence (EDA-NOCV) method shows that the strength of the N←Pt π interaction is not negligible …
Spin state, electronic structure and bonding on C-scorpionate [Fe(II)Cl2(tpm)] catalyst: An experimental and computational study
2020
Abstract The Fe(II) spin state in the condensed phase of [Fe(II)Cl2(tpm)] (tpm = [tris(pyrazol-1-yl)methane]; 1) catalyst has been determined through a combined experimental and theoretical investigation of X-Ray Absorption Spectroscopy (XAS) at the FeL2,3-edges and NK-edge. Results indicated that in this phase a mixed singlet/triplet state is plausible. These results have been compared with the already know Fe singlet spin state of the same complex in water solution. A detailed analysis of the electronic structure and bonding mechanism of the catalyst showed that the preference for the low-spin diamagnetic ground state, strongly depends upon the ligands, the bulk solvent and the interactio…
Comparative Experimental and Theoretical Study of the C and O K-Edge X-ray Absorption Spectroscopy in Three Highly Popular, Low Spin Organoiron Compl…
2019
The unoccupied electronic structures of three closed-shell, highly popular organoiron complexes ([Fe(CO)5], [(η5-C5H5)Fe(CO)(μ-CO)]2, and [(η5-C5H5)2Fe]; 0, I, and II, respectively) have been investigated both experimentally and theoretically by combining original gas-phase X-ray absorption spectroscopy (XAS) outcomes recorded at the C and O K-edge with results of scalar relativistic time-dependent density functional calculations carried out within the zeroth order regular approximation. Experimental evidence herein discussed complement the Fe L2,3-edges XAS ones we recently recorded, modeled, and assigned for the same complexes (Carlotto et al. Inorg. Chem. 2019, 58, 5844). The first-princ…
Bi3+doping in 1D ((CH3)3SO)PbI3: A model for defect interactions in halide perovskites
2022
The recently described monodimensional hybrid pseudo-perovskite ((CH3)3SO)PbI3 exhibits complete Pb2+/Bi3+ miscibility in the B site. Heterovalent substitution imposes that charge-compensating defects are introduced in the lattice as well. This paper reports the energetics of point defects and the interaction between charge-compensating defects that occur upon Bi3+ doping in ((CH3)3SO)PbI3. Periodic DFT simulations were employed to analyze the formation energy of Pb2+ vacancies, (CH3)3SO+ vacancies, iodide vacancies, or the insertion of interstitial iodide ions. Solid solutions with a large Bi3+ content were modeled considering different charge compensation defects (Pb2+ vacancies, (CH3)3SO…
Heterovalent BiIII/PbII ionic substitution in one-dimensional trimethylsulfoxonium halide pseudo-perovskites (X = I, Br)
2021
We report on the synthesis and characterization of novel lead and bismuth hybrid (organic-inorganic) iodide and bromide pseudo-perovskites (ABX3) containing the trimethylsulfoxonium cation (CH3)3SO+ (TMSO) in the A site, Pb/Bi in the B site, and Br or I as X anions. All of these compounds are isomorphic and crystallize in the orthorhombic Pnma space group. Lead-based pseudo-perovskites consist of one-dimensional (1D) chains of face-sharing [PbX6] octahedra, while in the bismuth-based ones, the chains of [BiX6] are interrupted, with one vacancy every third site, leading to a zero-dimensional (0D) local structure based on separated [Bi2I9]3- dimers. Five solid solutions for the iodide with di…
cis-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2, the poor relative between cis and trans tautomers. A theoretical study of the gas-phase Fe L3-edge and C and O K-edg…
2021
The relative stability of trans-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2 (trans-I) and cis-I tautomers in a vacuum and in solvents with different dielectric constants (e) has been investigated by exploiting density functional theory (DFT). Theoretical results indicate that, in agreement with experimental evidence, trans-I is more stable than cis-I in a vacuum (∼1.5 kcal mol−1; e = 1), while the opposite is true in media with e > 7. Differently from solution, DFT outcomes pertaining to the vapor-phase cis-I ⇆ trans-I equilibrium at T = 368 K, the temperature at which the Fe L2,3-edges and the C and O K-edge X-ray absorption spectroscopy (XAS) data of I have been recorded, ultimately indicate the trans-I …
Donation and back-donation in cis- and trans-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2 tautomers: Which relative is more generous? An ETS-NOCV bond analysis
2022
The ETS-NOCV bond analysis has been exploited to quantitatively estimate donation and back-donation properties of [(η5-C5H5)]−, CO, and FeI in the cis-/trans-[(η5-C5H5)Fe(η1-CO)(μ-CO)]2 (cis-I/trans-I) tautomers. Theoretical outcomes indicate that the Fe-CO bond, regardless to the CO monoapto (η1-) or bridging (μ-) coordination, has a sizeable π Fe → CO back-bonding contribution, which is stronger in trans-I than in cis-I. Moreover, [(η5-C5H5)]− has the weakest back-donation acceptor capability. The back-bonding behaviour of the Fe → η1-CO interaction well agrees with the experimental symmetric/antisymmetric infrared νCO (sνηjavax.xml.bind.JAXBElement@fc12185-CO/aνηjavax.xml.bind.JAXBElemen…
Cyclo- and Polyphosphazenes for Biomedical Applications
2022
Cyclic and polyphosphazenes are extremely interesting and versatile substrates characterized by the presence of -P=N- repeating units. The chlorine atoms on the P atoms in the starting materials can be easily substituted with a variety of organic substituents, thus giving rise to a huge number of new materials for industrial applications. Their properties can be designed considering the number of repetitive units and the nature of the substituent groups, opening up to a number of peculiar properties, including the ability to give rise to supramolecular arrangements. We focused our attention on the extensive scientific literature concerning their biomedical applications: as antimicrobial age…
A DFT mechanistic study of the synthesis of trans-Z,Z-[PtIICl(NH3){HN = C(NH2)Me}2]Cl from addition of NH3 to trans-[PtIICl2(N CMe)2]
2020
Abstract The reaction mechanism between trans-[PtIICl2(N CMe)2] and ammonia to give trans-Z,Z-[PtIICl(NH3){HN = C(NH2)Me}2]Cl has been studied at DFT level. Results showed that, in dichloromethane solution at 263.15 K, the chloride substitution by the ammonia on platinum is a process kinetically more favoured than the ammonia nucleophilic addition to the nitrile of about three orders of magnitude, and hence the nucleophilic addition reaction occurs after. Finally, both nucleophilic addition steps are geometrically driven to give products in the E configuration even if the final products were experimentally observed in the Z configuration. For trans-Z,Z-[PtIICl(NH3)(N CMe)2, the isomerizatio…
CCDC 2069442: Experimental Crystal Structure Determination
2021
Related Article: Candida Pipitone, Francesco Giannici, Antonino Martorana, Gonzalo Garc��a-Espejo, Silvia Carlotto, Maurizio Casarin, Antonietta Guagliardi, Norberto Masciocchi|2021|J.Phys.Chem.C|125|11728|doi:10.1021/acs.jpcc.1c02571
CCDC 2069441: Experimental Crystal Structure Determination
2021
Related Article: Candida Pipitone, Francesco Giannici, Antonino Martorana, Gonzalo Garc��a-Espejo, Silvia Carlotto, Maurizio Casarin, Antonietta Guagliardi, Norberto Masciocchi|2021|J.Phys.Chem.C|125|11728|doi:10.1021/acs.jpcc.1c02571
CCDC 2069440: Experimental Crystal Structure Determination
2021
Related Article: Candida Pipitone, Francesco Giannici, Antonino Martorana, Gonzalo Garc��a-Espejo, Silvia Carlotto, Maurizio Casarin, Antonietta Guagliardi, Norberto Masciocchi|2021|J.Phys.Chem.C|125|11728|doi:10.1021/acs.jpcc.1c02571
CCDC 2069439: Experimental Crystal Structure Determination
2021
Related Article: Candida Pipitone, Francesco Giannici, Antonino Martorana, Gonzalo Garc��a-Espejo, Silvia Carlotto, Maurizio Casarin, Antonietta Guagliardi, Norberto Masciocchi|2021|J.Phys.Chem.C|125|11728|doi:10.1021/acs.jpcc.1c02571