Complex plane impedance plots for Ba2PrRuO6 sample at different temperatures. The solid lines represent the fitting from the equivalent circuits.

Two thermally stable In-based MOFs exhibit high dielectric behavior with wide bandgaps.

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron‐donating (R=NH2) and electron‐withdrawing (R=NO2) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest‐free Zn‐based coordination polymers, [Zn(L1)(L2)]n (1) and [Zn(L1)(L3)]n (2) [L1=2‐(2‐pyridyl) benzimidazole (Pbim), L2=5‐aminoisophthalate (Aip), and L3=5‐nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH2 and NO2 substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO2 and NH2. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure‐dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.

Developing new semiconducting materials to meet the demands of modern high technology is an urgent issue. Here, we report on a zero-dimensional (0D) metal−organic complex semiconductor having a unique paddle-wheel nanostructure [Cu 6 (mpy) 6 ] n based on a compact Cu−S cage. Computational results suggest that this nanomaterial exhibits unique semiconducting behavior with a significant charge carrier separation upon excitation with a direct bandgap of 1.8 eV. Experimental measurements including AC conductivities as well as diffuse reflection spectra confirmed its bandgap properties (1.9 eV), which are comparable to bandgaps for other commonly available semiconducting materials. The overall findings reveal that this Cu-based paddle-wheel metal−organic complex represents a promising 0D semiconductor with a unique structural architecture and has significant electronic features. The findings presented in this study promise to open up a new pathway that could lead to the development of metal−organic complexes containing shapedependent semiconducting behavior.