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Keywords = cryogenic photodissociation

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13 pages, 1918 KiB  
Article
A DFT and Matrix–Isolation IR/UV-Visible Study of High-Coordinated Lanthanide-CO Complexes
by Attila Kovács and Werner Klotzbücher
Molecules 2023, 28(13), 5043; https://doi.org/10.3390/molecules28135043 - 28 Jun 2023
Cited by 2 | Viewed by 1720
Abstract
Recent joint mass spectrometric and IR photodissociation studies have provided proof on the existence of octa-coordinated ionic lanthanide-carbonyl complexes under those extreme gaseous conditions. In contrast, in older literature concerning cryogenic studies of neutral Ln(CO)x species, the highest coordination was assigned to [...] Read more.
Recent joint mass spectrometric and IR photodissociation studies have provided proof on the existence of octa-coordinated ionic lanthanide-carbonyl complexes under those extreme gaseous conditions. In contrast, in older literature concerning cryogenic studies of neutral Ln(CO)x species, the highest coordination was assigned to hexa-coordinated Ln(CO)6 molecules. The present study aims to clarify the above controversy using matrix isolation spectroscopy and DFT calculations. In order to ensure the maximum possible coordination, the Ln(CO)x complexes were synthesized in neat CO cryogenic matrices at 10 K and were investigated by infrared and UV-visible spectroscopy. The formed complexes were identified on the basis of the characteristic CO stretching frequencies of the ground-state molecules predicted by DFT calculations. Our joint experimental–theoretical analysis confirmed the preference of octa-coordinated Ln(CO)8 complexes in cryogenic neat CO matrices. Full article
(This article belongs to the Section Molecular Structure)
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15 pages, 4328 KiB  
Review
Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids
by Ivana Biljan and Hrvoj Vančik
Crystals 2017, 7(12), 376; https://doi.org/10.3390/cryst7120376 - 14 Dec 2017
Cited by 13 | Viewed by 7962
Abstract
This review is focused on the dimerization and dissociation of aromatic C-nitroso compounds and their dimers, the reactions that could be used as a convenient model for studying the thermal organic solid-state reaction mechanisms. This molecular model is simple because it includes formation [...] Read more.
This review is focused on the dimerization and dissociation of aromatic C-nitroso compounds and their dimers, the reactions that could be used as a convenient model for studying the thermal organic solid-state reaction mechanisms. This molecular model is simple because it includes formation or breaking of only one covalent bond between two nitrogen atoms. The crystalline molecular solids of nitroso dimers (azodioxides) dissociate by photolysis under the cryogenic conditions, and re-dimerize by slow warming. The thermal re-dimerization reaction is examined under the different topotactic conditions in crystals: disordering, surface defects, and phase transformations. Depending on the conditions, and on the molecular structure, aromatic C-nitroso compounds can associate to form one-dimensional polymeric structures and are able to self-assemble on gold surfaces. Full article
(This article belongs to the Special Issue Photocrystallography and Solid-State Structural Dynamics)
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