Macrocyclic Zn^II and Cu^II complexes as guests of the hybrid composites based on the layered MnPS₃ phase. Comparison of spectroscopic properties

Abstract

A family of macrocyclic complexes [M 2 L n Cl 2 ] have been synthesized and characterized (M: Cu II or Zn II ; L n : macrocyclic ligand derived from 2-hydroxy-5-methyl-1,3-benzenedicarbaldehyde and different aliphatic diamines and o-phenylenediamine). The influence of the aromaticity of the ligand and the metal center on the spectroscopic properties of the complexes (absorption and emission) has been studied. Making use of the weak interactions between hydrated potassium ions and the layers of the K 0.4 Mn 0.8 PS 3 precursor, the obtained macrocyclic complexes have been intercalated in the interlamellar space by a microwave assisted cationic exchange reaction. The optical properties of the obtained hybrid materials are reported. The absorption edge, recorded by solid state reflectance spectroscopy for Cu II and the Zn II macrocycle-based composites, is 1.67-1.76 eV, both shifted to lower energy compared with that of the pristine MnPS 3 .

Magnetic properties of composites based on the intercalation of ZnII and CuII bimetallic macrocyclic complexes in the MnPS3 phase

“…14Å and a width of 10-13Å, depending on the lateral amines, it is possible to assume that the macrocyclic species in the nal composites are parallel to the layers. 7 In conclusion, there will be an interaction between the free axial positions of the metal centers in the complex and the protruding sulphur atoms in the layers, as shown in Scheme 2. Because the distance between the metal centers in the macrocyclic complexes is ca.…”

“…The intercalation of these complex species in the interlamellar space produces composites with different properties in comparison with those of the precursor K 0.4 Mn 0.8 PS 3 $H 2 O. 3,7,15 The precursors and composites were characterized by FTIR spectroscopy. The pristine MnPS 3 phase displays only one vibration band at 570 cm À1 , which is attributed to PS 3 groups, and a weak band at 450 cm À1 due to P-P bonds.…”

“…3,[11][12][13][14][15] Many synthetic pathways have been developed for intercalating different species. 1,7,[16][17][18][19][20] One of the most widely used is ionic exchange, in which the guest is a cation such as potassium, lithium, tetramethylammonium, or the 4-[2-(4-dimethylaminophenyl) ethenyl]-1-methylpyridinium cation (DAMS + ), among others. In this process, the charge of the guest is balanced by the partial removal of manganese(II) ions from the lamellar host, 19 which gives rise to different composites of the formula M I 2x Mn (1Àx) -PS 3 .…”

“…This procedure enables the preparation of useful precursors such as K 0.4 Mn 0.8 PS 3 $H 2 O, which is a well-known phase used for further intercalation reactions of bulky guests such as macrocyclic complexes. 3,7,9,15,21 In addition, the K 0.4 Mn 0.8 PS 3 -$H 2 O phase exhibits spontaneous magnetization, which has been explained by ordered vacancies present along the lamellae. 22,23 It is due to this interesting magnetic phenomenon and the lability of the interlamellar potassium ions that the K 0.4 Mn 0.8 PS 3 $H 2 O phase has been widely studied and is still being utilized to obtain new composites.…”

New dinuclear zinc(ii) complexes with Schiff bases obtained from o-phenylenediamine and their application as fluorescent materials in spin coating deposition

“…12 It is also known, that the d 10 conguration of the zinc(II) cation results of the occurrence only MLCT, LMCT or p / p* ligand based transitions regarding the spectroscopy and photochemistry of zinc(II) compounds. [13][14][15][16][17] Moreover, the type of an amine used 22 and signicance of the rst coordination sphere of the central atom are responsible for the emission properties of the isolated compounds. 18,19 Therefore the main factor, which allows to control the luminescence properties of complexes can be design of the Schiff bases part of the complexes.…”