New classes of tridentate N-donor rhodium(I) complexes have been synthesized and demonstrated to exhibit interesting induced self-assembly behavior by variation of external stimuli, as a result of extensive Rh(I)center dot center dot center dot Rh(I) interactions, with the assistance of pi-pi stacking and hydrophobic-hydrophobic interactions. An isodesmic aggregation mechanism has also been identified in the temperature dependent process. Upon aggregation in acetone solution, the complex molecules form wire-like nanostructures with their shape dependent on the pi-conjugation of the tridentate ligands. On the other hand, crystalline needles of rhodium(I) complexes obtained from recrystallization have also been shown to exhibit conductivity on the order of 10(-3) S cm(-1).