Large dielectric constant and band
gap are essential for insulating materials used in applications such
as capacitors, transistors and photovoltaics. Of the most common polymers
utilized for these applications, polyvinyldiene fluoride (PVDF) offers
a good balance between dielectric constant, >10, and band gap,
6 eV, but suffers from being a ferroelectric material. Herein, we
investigate a series of aliphatic organotin polymers, p[DMT(CH<sub>2</sub>)<i><sub>n</sub></i>], to increase the dipolar and
ionic part of the dielectric constant while maintaining a large band
gap. We model these polymers by performing first-principles calculations
based on density functional theory (DFT), to predict their structures,
electronic and total dielectric constants and energy band gaps. The
modeling and experimental values show strong correlation, in which
the polymers exhibit both high dielectric constant, ≥5.3, and
large band gap, ≥4.7 eV with one polymer displaying a dielectric
constant of 6.6 and band gap of 6.7 eV. From our work, we can identify
the ideal amount of tin loading within a polymer chain to optimize
the material for specific applications. We also suggest that the recently
developed modeling methods based on DFT are efficient in studying
and designing new generations of polymeric dielectric materials