The energy difference between the highest molecular orbital (HOMO annotated as E H ) and the lowest unoccupied molecular orbital (LUMO annotated as E L ), being abbreviated as ΔE HL , is commonly used to characterize the fundamental electronic properties of molecules. For instance, the electrical resistivity of molecules is generally considered to be directly proportional to ΔE HL . The size of ΔE HL could be quantitatively determined by the various experimental or theoretical approachesthe electrochemical oxidation/reduction potential measurements or the optimized wavefunctions governed by ab initio electronic structure calculations. The absolute values of E H and E L are derived by the explicit inter-particle interactions between electrons and atomic nuclei. Synthetic chemistry has a long history in developing the molecular structure diversity, leading to the ideal molecular electronic properties for the specific chemical applications. Understand the interplay between molecular structures and electronic properties plays a critical role to the pace of these scientific developments. Despite the quantum chemical calculation based approaches have been popularly adopted to investigate the insights of the molecular structure diversities, a computationally efficient-and-interpretable approach is the interest of chemistry community for addressing the unlimited possibility of molecular architectures.