Magnetic behavior of MnPS 3 phases intercalated by [Zn 2 L] 2 þ (LH 2 : macrocyclic ligand obtained by condensation of 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde and 1,2-diaminobenzene) E. Spodine a,b,n , P. Valencia-Ga ´ lvez b,c , P. Fuentealba a,b , J. Manzur b,c , D. Ruiz a , D. Venegas-Yazigi b,d , V. Paredes-Garcı ´a b,e , R. Cardoso-Gil f , W. Schnelle f , R. Kniep f a Facultad de Ciencias Quı ´micas y Farmace´uticas, Universidad de Chile, Chile b Centro para el Desarrollo de Nanociencia y Nanotecnologı ´a, Cedenna, Chile c Facultad de Ciencias Fı ´sicas y Matema ´ticas, Universidad de Chile, Chile d Facultad de Quı ´mica y Biologı ´a, Universidad de Santiago de Chile, Chile e Departamento de Quı ´mica, Universidad Tecnolo ´gica Metropolitana, Chile f Max-Planck-Institut fur Chemische Physik fester Stoffe, Germany article info Article history: Received 13 September 2010 Received in revised form 27 January 2011 Accepted 3 March 2011 Available online 21 March 2011 Keywords: Intercalated MnPS 3 phase Binuclear Zn(II) macrocyclic complex Magnetic properties Microwave assisted synthesis abstract The intercalation of the cationic binuclear macrocyclic complex [Zn 2 L] 2 þ (LH 2 : macrocyclic ligand obtained by the template condensation of 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde and 1,2-diaminobenzene) was achieved by a cationic exchange process, using K 0.4 Mn 0.8 PS 3 as a precursor. Three intercalated materials were obtained and characterized: (Zn 2 L) 0.05 K 0.3 Mn 0.8 PS 3 (1), (Zn 2 L) 0.1 K 0.2 Mn 0.8 PS 3 (2) and (Zn 2 L) 0.05 K 0.3 Mn 0.8 PS 3 (3), the latter phase being obtained by an assisted microwave radiation process. The magnetic data permit to estimate the Weiss temperature y of E 130 K for (1); E 155 K for (2) and E 130 K for (3). The spin canting present in the potassium precursor remains unperturbed in composite (3), and spontaneous magnetization is observed under 50 K in both materials. However composites (1) and (2) do not present this spontaneous magnetization at low temperatures. The electronic properties of the intercalates do not appear to be significantly altered. The reflectance spectra of the intercalated phases (1), (2) and (3) show a gap value between 1.90 and 1.80 eV, lower than the value observed for the K 0.4 Mn 0.8 PS 3 precursor of 2.8 eV. & 2011 Elsevier Inc. All rights reserved. 1. Introduction The study of materials with lamellar structure has been generating a great interest over the past years due to their anisotropic physical properties. Materials with such a lamellar structure permit to host a wide range of guests, such as organic compounds [1,2], organometallics [3], polymers [4,5], and mono- valent and trivalent cations [6–9]. This intercalation chemistry allows to obtain new materials in which the host properties are significantly modified. For example, nonlinear optic materials [1,9,10], magnetic materials [3,11,12], catalysts [13], electroactive materials [14], multifunctional [15,16] and new dielectric materi- als [17,18] are obtained by the intercalation of one of the above mentioned guests. Transition-metal thiophosphate MPS 3 ,(M¼ Mn, Cd) present an inorganic lamellar structure, which can be described by analogy to the layered structure of the CdCl 2 type [19–21]. The electric and magnetic properties reported for MnPS 3 and CdPS 3 indicate a semiconductor character with low values of conductivity [22], and antiferromagnetic and diamagnetic properties, respectively [23]. The manganese and cadmium chalcogenides MPS 3 allow intercalation of voluminous guests through a cationic transfer processes followed by a cationic exchange [3,24]. An alternative synthetic route in order to obtain these com- pounds is the intercalation assisted by microwave radiation. This synthetic approach is largely used in organic chemistry, for example, in esterification, hydrolysis, and substitution reactions [25]. However, this alternative synthetic method is less used in inorganic reactions, except for reports for the use of microwaves in the intercalation of organic species in V 2 O 5 [26], in the mixed oxide a-VO(PO 4 ) [27], in FePS 3 and in Fe 0.86 Mn 0.18 PS 3 [28]. For the intercalation of coordination compounds in lamellar materials, literature reports the composites formed by Mn(III), Fe(III), and Contents lists available at ScienceDirect journal homepage: www.elsevier.com/locate/jssc Journal of Solid State Chemistry 0022-4596/$ - see front matter & 2011 Elsevier Inc. All rights reserved. doi:10.1016/j.jssc.2011.03.009 n Corresponding author at: Facultad de Ciencias Quı ´micas y Farmace ´ uticas, Universidad de Chile, Chile. E-mail address: espodine@uchile.cl (E. Spodine). Journal of Solid State Chemistry 184 (2011) 1129–1134