A donor-pi-acceptor strategy is being well exploited in several fields in view of their robust optical properties. However, the impact of branching in quadrupolar [A-(pi-D)(2)] and octupolar [A-(pi-D)(3)] molecules in comparison to parent dipolar (A-pi-D) molecules on the delayed fluorescence and phosphorescence properties is seldom explored. We have presented herein the distinct and contrasting optical properties of a tridurylborane core bearing -NH2 (1-3) and -NMe2 (4-6) donor moieties, wherein the number of donors is increased systematically. Because of propeller molecular architecture, the donor and acceptor are weakly coupled, and the frontier molecular orbitals are spatially localized. All of the compounds show delayed fluorescence under ambient conditions and persistent phosphorescence at low temperature. Solvent-dependent studies and temperature-dependent luminescence measurements established that quadrupolar (2 and 5) and octupolar (3 and 6) compounds underwent symmetry breaking in the excited state. Curiously, delayed fluorescence and phosphorescence spectra are found to be blue-shifted and follow the same trend as the fluorescence upon an increase in the branches. The highest quantum yield was observed for dipolar compounds. Besides, the phosphorescence lifetime decreases with an increase in the number of branches. These interesting experimental observations are further supported by quantum-mechanical calculations.