3D-2D lattice dimensionality, optical Eg and PL energy variations due to organic variant in two [ZnCl4]2- based hybrid materials

Abstract

Single crystal growth of two inorganic-organic compounds, Bis[2-methylpyridine tetrachlorozincate] (MPCZ) and Bis[2-amino-5-chloropyridine tetrachlorozincate] (ACPCZ) has been achieved by two different methods i.e. Gel growth and Solution growth through slow cooling process. Due to change in organic moiety, the single crystal growth of ACPCZ could not be achieved by gel growth method whereas solution growth through slow cooling process results the single crystals of ACPCZ. Different physiochemical characterization techniques like single crystal XRD, UV–Vis spectroscopy, FESEM image analysis, luminescence property, etc. shows structure stability with charge assisted secondary interactions, lattice dimensionality (3D-2D) and interweaving design of two inorganic-organic hybrid materials. In MPCZ hybrid derivative, organic moiety form 3D spreader shape pattern and the inorganic moiety link the train of spreaders along ac-plane whereas the change in organic moiety in ACPCZ has 2D shear grade pattern of inorganic-organic components along b-axis with steepness grade of 1.29 Å and angle of inclination of 49.5°. The surface study of the hybrid materials indicate the average granular size of 28 nm for MPCZ whereas the image of ACPCZ shows variation in spatial parameters of average granular size of 60 nm due to alteration of organic derivative from 2-methylpyridine to 2-amino-5-chloropyridine. The change in optical energy direct band gap value from 3.01eV for MPCZ to 3.42eV for ACPCZ indicates the role of organic compounds in optical properties of hybrid materials. The photoluminescence energies and band gap electronic transitions were investigated with Photoluminescence emission spectra presents that the excitation energy changes from 2.83 eV to 2.06 eV in MPCZ and 2.80 eV–2.14 eV in ACPCZ.