TY - JOUR

T1 - Photogeneration of Several Linkage Isomers and Investigation of Forward and Backward Nitro-Nitrito Isomerization Processes in a Palladium Complex

AU - Mikhailov, Artem

AU - Konieczny, Krzysztof A

AU - Gladysheva, Maria

AU - Plyusnin, Pavel

AU - Pillet, Sébastien

AU - Schaniel, Dominik

N1 - ACKNOWLEDGMENTS: The work has been supported by grant of ANR (grant no. ANR-21-CE30-0045-01). A.M. is grateful for financial support from the Metchnikov bourse program 2021. We thank the PMD2X platform of Université de Lorrain for granting access to XRD diffractometers.

PY - 2023/4/10

Y1 - 2023/4/10

N2 - Photoinduced linkage isomers (PLIs) of the nitro-ligand were generated and comprehensively characterized in a square planar unit [Pd(NH3)3NO2]+ of the complex salts [Pd(NH3)4][Pd(NH3)3NO2][MOx3]·yH2O (M = Cr (Cr), Rh (Rh), Co (Co), Ox = oxalate). Structural (XRD) and spectroscopic (IR, UV-vis) investigations at 10 and 150 K allowed determining the structures of several photoinduced linkage isomers, endo-ONO (PLI1, 2) and exo-ONO (PLI3, 4) isomers generated by irradiation with 365 nm from the initial NO2 (GS), along with the assignment of the infrared (IR) bands to each structural isomer. Based on a combination of these methods, the photo- and thermally induced interplay of PLIs was investigated. Irradiation in the temperature range of 10-80 K induces the formation of both endo- and exo-ONO isomers, while increasing the temperature up to 150 K results in the formation of only endo-ONO isomers. The structural arrangement of the endo-ONO and exo-ONO PLI is strongly influenced by intermolecular interactions due to the partial occupation of a neighboring site by water molecules. The investigation of thermal dynamics of PLIs revealed that the thermal decay of the exo-ONO isomer occurs via two steps exo-ONO → endo-ONO → NO2. The kinetic parameters (Ea, k0) of both decay processes were determined together with the characteristic decay temperatures (Td) by IR spectroscopy. According to the photoinduced dynamics measured by IR spectroscopy, the mechanism of PLI formation in [Pd(NH3)3NO2]+ could be described as NO2 → endo-ONO → exo-ONO.

AB - Photoinduced linkage isomers (PLIs) of the nitro-ligand were generated and comprehensively characterized in a square planar unit [Pd(NH3)3NO2]+ of the complex salts [Pd(NH3)4][Pd(NH3)3NO2][MOx3]·yH2O (M = Cr (Cr), Rh (Rh), Co (Co), Ox = oxalate). Structural (XRD) and spectroscopic (IR, UV-vis) investigations at 10 and 150 K allowed determining the structures of several photoinduced linkage isomers, endo-ONO (PLI1, 2) and exo-ONO (PLI3, 4) isomers generated by irradiation with 365 nm from the initial NO2 (GS), along with the assignment of the infrared (IR) bands to each structural isomer. Based on a combination of these methods, the photo- and thermally induced interplay of PLIs was investigated. Irradiation in the temperature range of 10-80 K induces the formation of both endo- and exo-ONO isomers, while increasing the temperature up to 150 K results in the formation of only endo-ONO isomers. The structural arrangement of the endo-ONO and exo-ONO PLI is strongly influenced by intermolecular interactions due to the partial occupation of a neighboring site by water molecules. The investigation of thermal dynamics of PLIs revealed that the thermal decay of the exo-ONO isomer occurs via two steps exo-ONO → endo-ONO → NO2. The kinetic parameters (Ea, k0) of both decay processes were determined together with the characteristic decay temperatures (Td) by IR spectroscopy. According to the photoinduced dynamics measured by IR spectroscopy, the mechanism of PLI formation in [Pd(NH3)3NO2]+ could be described as NO2 → endo-ONO → exo-ONO.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85151389458&origin=inward&txGid=5f1792cbf0041f1d7df5857b6e966997

UR - https://www.mendeley.com/catalogue/8c80e909-455f-3905-ad9e-47063fc440ee/

U2 - 10.1021/acs.inorgchem.3c00028

DO - 10.1021/acs.inorgchem.3c00028

M3 - Article

C2 - 36989116

VL - 62

SP - 5531

EP - 5542

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 14

ER -