Structure-property correlations in rubrene (RB) colloidal J-aggregates were unravelled by steady state and time resolved spectroscopy in conjunction with excited state density functional calculations. The RB J-aggregate with a slippage angle theta=30.4 degrees, estimated from the monomeric transition dipole moment directions, exhibited a broad fwhm of 1073 cm(-1) and a 5 nm red-shifted absorption band carrying a transition dipole moment ((M) over right arrow (lambda agg)= 1.80 D) almost equivalent to the monomeric dye ((M) over right arrow (lambda mon) = 1.89 D). A significantly low magnitude of exciton coupling energy, Delta E-exc = -358 cm(-1) for the rhombic-RB colloidal J-aggregates resulted owing to the weaker electronic communication between the largely separated RB subunits (r = 7.2 (A) over circle) and a restricted exciton delocalization over the RB J-dimer (N = 2). The RB J-dimer exhibited a perfect balance between the computed singlet (2.53 eV) and the triplet (1.29 eV) exciton energies for singlet fission (SF). Supporting this, the PL decay profile of the J-aggregates revealed a delayed fluorescence, substantiating triplet pair formation via SF. The experimental evidence for the longlived triplet formation was furthermore confirmed by its transient absorption (T-1 -> T-N) at 530 nm. Consequently, a high probability for SF and a low probability for triplet-triplet recombination, leading to a dramatic lowering in photoluminescence quantum yield from 0.172 down to 0.035 was noted. The electronic structure calculations for the RB J-dimer followed TD-DFTM062X/6-31G+(d,p) level of theory following integral equation formalism polarizable continuum model (IEFPCM) in water. S-1 excited state for RB J-dimer was carefully analyzed using integral overlap of electron and hole density distribution (phi) and the defined t-indexes along all three spatial directions, and was found to be of locally excited in character.