A series of novel neutral mononuclear rhodium(I) complexes of the P?NH ligands have been prepared starting from [Rh(cod)Cl](2) complex. Structural elucidation of the complexes was carried out by elemental analysis, IR and multinuclear NMR spectroscopic data. The complexes were applied to the transfer hydrogenation of acetophenone derivatives to 1-phenylethanol derivatives in the presence of 2-propanol as the hydrogen source. Catalytic studies showed that all complexes are also excellent catalyst precursors for transfer hydrogenation of aryl alkyl ketones in 0.1m iso-PrOH solution. In particular, [Rh(cod)(PPh2NH?C6H4?4-CH(CH3)(2))Cl] acts as an excellent catalyst, giving the corresponding alcohols in excellent conversion up to 99% (turnover frequency588h(-1)). Furthermore, rhodium(I) complexes have been used in the formation of organic-inorganic heterojunction by forming their thin films on n-Si and evaporating Au on the films. It has been seen that the structures have rectifying properties. Their electrical properties have been analyzed with the help of current-voltage measurements. Finally, it has been shown that the complexes can be used in the fabrication of temperature and light sensors. Copyright (c) 2014 John Wiley & Sons, Ltd.