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Updated: Sep 27, 2026
Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
Published on: June 7, 2018
Metal-dependent ferro- versus antiferromagnetic interactions in molecular crystals of square Planar (M(II)
Mohammed Fettouhi1, Bassam El Ali, Mohammed Morsy
1Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia. fettouhi@kfupm.edu.sa
Abstract:
The synthesis and structural, spectral, and magnetic characterizations of two new complexes of formula [Pt(IM(2)Py)Cl(2)] (A) and [Pd(IM(2)Py)Cl(2)] (B) are reported. IM(2)Py 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 (P2(1)/n) [P2(1)/c], a = 7.906(2) [7.989(3)] A, b = 17.872(9) [10.168(4)] A, c = 10.357(3) [17.623(6)] A, beta = 90.732(13) degrees [95.940(2)] degrees, Z = 4 [4]. Structural parameters for B: T = 293 K [120 K], monoclinic (P2(1)/n) [P2(1)/c], a = 7.900(3) [7.9730(2)] A, b = 17.907(9) [10.1806(3)] A, c = 10.299(3) [17.7171(4)] A, beta = 90.524(14) degrees [95.747(2)] degrees, 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)] A and 2.015(7) [2.029(8)], 2.287(3) [2.294(3)] A, 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.
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