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Metal-dependent ferro- versus antiferromagnetic interactions in molecular crystals of square planar {M(II) imino-nitroxide radical} complexes (M = Pt, Pd)

hal.structure.identifierInorganic Chemistry Laboratory-Faculty of Chemistry
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorTANASE, Stefania
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierInstitute of Physical Chemistry
dc.contributor.authorTUNA, Floriana
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorGUIONNEAU, Philippe
hal.structure.identifierInorganic Chemistry Laboratory-Faculty of Chemistry
dc.contributor.authorMARIS, Thierry
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorROMBAUT, Guillaume
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorMATHONIÈRE, Corine
hal.structure.identifierInorganic Chemistry Laboratory-Faculty of Chemistry
dc.contributor.authorANDRUH, Marius
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorKAHN, Olivier
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorSUTTER, Jean-Pascal
dc.date.issued2003
dc.identifier.issn0020-1669
dc.description.abstractEnThe synthesis and structural, spectral, and magnetic characterizations of two new complexes of formula [Pt(IM2Py)Cl2] (A) and [Pd(IM2Py)Cl2] (B) are reported. IM2Py stands for the imino-nitroxide radical ligand 2-(ortho-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl. Their crystal structures were solved at room temperature and at 120 K revealing structural phase transitions from pseudo-orthorhombic to monoclinic systems for the two compounds which remain isostructural in the whole temperature range explored. Structural parameters for A: T = 293 K [120 K], monoclinic (P21/n) [P21/c], a = 7.906(2) [7.989(3)] Å, b = 17.872(9) [10.168(4)] Å, c = 10.357(3) [17.623(6)] Å, = 90.732(13) [95.940(2)], Z = 4 [4]. Structural parameters for B: T = 293 K [120 K], monoclinic (P21/n) [P21/c], a = 7.900(3) [7.9730(2)] Å, b = 17.907(9) [10.1806(3)] Å, c = 10.299(3) [17.7171(4)] Å, = 90.524(14) [95.747(2)], Z = 4 [4]. In both complexes, the metal coordination is essentially planar. The average Pt-N, Pt-Cl and Pd-N, Pd-Cl bond lengths are 1.996(6) [1.88], 2.295(2) [2.248(8)] Å and 2.015(7) [2.029(8)], 2.287(3) [2.294(3)] Å, respectively. The solid state structure is characterized by a pairlike molecular packing stacked in columns parallel to the a axis; this dimer character is reinforced at low temperature. Despite their structural similarity, the investigation of the magnetic properties revealed that dominant ferromagnetic interactions govern the behavior of the Pt derivative A, whereas antiferromagnetic interactions take place for the Pd compound B. A rationalization for this rather intriguing difference is proposed in light of the spin population deduced from density functional theory calculations. The electronic absorption spectra of A and B present structured absorption bands in the visible which are attributed to MLCT transitions. Both compounds are nonluminescent at room temperature. However, a weak emission is detected for A in butyronitrile glasses at 77 K, indicating that the MLCT excited state is strongly quenched at low temperature.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.subjectLuminescence
dc.subjectFerromagnetic exchange
dc.subjectAntiferromagnetic exchange
dc.subjectStructural phase transition
dc.subjectCrystal structure
dc.subjectMolecular structure
dc.subjectExchange interaction
dc.subjectLuminescence quenching
dc.title.enMetal-dependent ferro- versus antiferromagnetic interactions in molecular crystals of square planar {M(II) imino-nitroxide radical} complexes (M = Pt, Pd)
dc.typeArticle de revue
dc.identifier.doi10.1021/ic0255813
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page1316-1321
bordeaux.volume42
bordeaux.issue4
bordeaux.peerReviewedoui
hal.identifierhal-00258363
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00258363v1
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