Abstract
A novel cation-stabilized iodocuprate, named {CuI3](1,6-bpx)}1), [1,6-bpx = 1,6-bis(pyridinium)xylol] have been constructed from mixtures of bis(pyridinium) xylol and cuprous iodide in acetonitrile solution. Compound
Introduction
As in past decades, much interest in recognition of the supramolecules has undergone a rapid development and has attracted considerable attention due to their fascinating structures and functionalities such as magnetism, molecular recognition, sensors, materials science, electrical conductivity, biology, optical properties, host-guest properties and catalysis [1–4]. Among the numerous families of supramolecular compounds, the family directed by organic cations with azotic heterocycles has occupied a crucial position in the chemical engineering and molecular science [5, 6]. The geometries of organic cations play an essential role in the construction of novel supramolecular complexes, and so much effort has been devoted to the design and modification of the organic cations to control the products [7–9]. To date, plenty of heterocyclic nitrogen-containing organic cations have been widely used to construct supramolecular compounds with exciting structure and novel properties [10, 11]. Among them, isoquinoline derivatives refer to isoquinoline itself, are paid close attention because of their broad range of biological activities [12–15]. However, only a few have been made from halogenmetallates with isoquinoline derivatives, such as Song et al. have studied an iodocuprate of 1,4-bip and the thermal properties [16].
As an extension of this study, we carried out the reactions of CuI with 1,6-bpx, and a new halogencuprate complex with the 1,6-bpx dication, [1,6-bpx] [CuX3] was obtained therefrom. Herein we report its syntheses, crystal structure, chemical and thermal properties.
Experimental
Materials and methods
The dication 1, 6-bis(pyridinium)xylol was prepared as the bromide salt by direct alkylation of pyridine with 1,4-bis-bromomethyl-benzene and acetonitrile served as the solvent for the reaction. The reaction route was shown in (Scheme 1). Other chemicals were obtained from commercial sources and used as received without further purification. The IR spectrum was recorded on a Shimazu IR435 spectrometer as KBr disk(4000–400 cm–1). Powder X-ray-diffraction (PXRD) measurements were performed on a Scintag X1 diffractometer with Cu–Kα (λ= 1.5418 Å) at 50 kV, 200 mA with a 2θ range of 4–40° at room temperature. A model NETZSCHTG209 thermal analyzer was used to record simultaneous TG curves in the flowing nitrogen atmosphere of 20 mL min–1 at a heating rate of 5°C min–1 in the temperature range r. t.–900°C using platinum crucibles. The photoluminescent spectra were performed on a Hitachi F-4500 spectrofluorometer.
Synthesis of the 1, 6-bpx cation.
[CuI3](1,6-bpx)
X-ray crystallography study
X-ray diffraction data for
Crystal data details for 1
Crystal data details for
Description of crystal structure
In the title compound, (1, 6-bpx)[CuI3], the asymmetric unit contains a 1, 6-bpx cation and a CuI3 anion (Fig. 1(a)). In the anion, Cu-I bond distances lie in the range of 2.548–2.556Å. All of the atoms in the anion are essentially coplanar. In the crystal structure, an extensive network of C–H⋯I hydrogen bonds links the cations and anions into an extended three-dimensional network, with the cations further aggregated through – stacking interactions (Fig. 1(b)). Other bond angle and lengths are compared with those found in the organic cation stabilized iodocuprate analogues [18, 19]. Under the dual action of hydrogen bond and electrostatic interaction, inorganic mononuclear anions are evenly distributed in the voids of cations which arranged in a regular and orderly manner (Fig. 1(c)).
(a) The perspective view of the structure of
Figure 2 shows the absorption spectra of
Absorption spectra of 1,6-bpx and
PXRD patterns of
In order to investigate the thermal decomposition behavior of compound
TG plots of compound
The synthesis of a new iodocuprate complexes of 1,6-bpx has been achieved via a direct method of complexation in solution. The new supramolecular system is chemical and thermally stable and has been characterized by X-ray crystallography. The complex has a monomeric structure in the solid state. Investigation of the use of the new cuprous complex as a luminescent agent is underway and will be reported in due course.