Synthesis, structure, and photophysical properties of platinum(II) (N, C, N) pincer complexes derived from purine nucleobases

Lorenzo-Aparicio, C. ; Moreno-Blázquez, S. (Universidad de Zaragoza) ; Oliván, M. ; Esteruelas, M. A. ; Gómez Gallego, M. ; García-Álvarez, P. ; Cabeza, J. A. ; Sierra, M. A.

Resumen: The synthesis of a series of Pt{κ3-N,C,N′-[L]}X (X = Cl, RC≡C) pincer complexes derived from purine and purine nucleosides is reported. In these complexes, the 6-phenylpurine skeleton provides the N,C-cyclometalated fragment, whereas an amine, imine, or pyridine substituent of the phenyl ring supplies the additional N′-coordination point to the pincer complex. The purine N,C-fragment has two coordination positions with the metal (N1 and N7), but the formation of the platinum complexes is totally regioselective. Coordination through the N7 position leads to the thermodynamically favored [6.5]-Pt{κ3-N7,C,N′-[L]}X complexes. However, the coordination through the N1 position is preferred by the amino derivatives, leading to the isomeric kinetic [5.5]-Pt{κ3-N1,C,N′-[L]}X complexes. Extension of the reported methodology to complexes having both pincer and acetylide ligands derived from nucleosides allows the preparation of novel heteroleptic bis-nucleoside compounds that could be regarded as organometallic models of Pt-induced interstrand cross-link. Complexes having amine or pyridine arms are green phosphorescence emitters upon photoexcitation at low concentrations in CH2Cl2 solution and in poly(methyl methacrylate) (PMMA) films. They undergo self-quenching at high concentrations due to molecular aggregation. The presence of intermolecular π–π stacking and weak Pt···Pt interactions was also observed in the solid state by X-ray diffraction analysis.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.3c00650

Año: 2023

Publicado en: Inorganic Chemistry 62, 21 (2023), 8232-8248
ISSN: 0020-1669

Factor impacto JCR: 4.3 (2023)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 8 / 44 = 0.182 (2023) - Q1 - T1

Factor impacto CITESCORE: 7.6 - Inorganic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1)

Factor impacto SCIMAGO: 0.928 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2019-104652GB-I00
Financiación: info:eu-repo/grantAgreement/ES/DGA/E06-23R
Financiación: fo:eu-repo/grantAgreement/ES/DGA-FSE/LMP23-21
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2019-108429RB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RED2018-102387-T

Tipo y forma: Article (Published version)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)