- Sequential self-assembly of a two-component system on a solid support is described with respect to structure and function. Two ligands, which bind to the semiconductor surface through one end and axially ligate a heme analogue at the other end, are described. Monolayer assemblies of complexes formed by these ligands and iron-porphyrin perform reversible binding of molecular oxygen. In the monolayer, a metalloporphyrin (the sensing unit) is held by the intervening ligand that serves as a “hinge”, away from the solid surface. Sensing events based on porphyrin chemistry are communicated via the ligand to the solid support. The transduction manifests itself as a change in the solid's surface electronic properties. Synthesis of the ligands and analysis of its complex formation with FeIII-porphyrin are described. The anisotropic orientation of the porphyrin ring within the ligand cavity, due to restricted rotation around the FeIII−N imidazole bonds, was probed by 1H NMR measurements in solution. We show that the porphyrin substituents stand as barriers for the free rotation even at room temperature. Molecular modeling supports the NMR evidence and reveals the stable conformations for the porphyrin's orientation relative to the solid support. The complexes were assembled as films on the (0001) surface of etched n-CdSe single crystals, and the films were characterized using transmission Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopies. Contact potential difference (CPD) and steady-state photoluminescence (PL) measurements of the derivatized CdSe show that the intervening ligands yield better conjugation and stronger binding of the sensing unit to the semiconductor surface, relative to direct adsorption of metalloporphyrins. Furthermore, the PL changes in the CdSe can be used to follow the interaction of the surface-bound FeIII-porphyrin−ligand complexes with molecular oxygen. A model is proposed to explain the electronic changes resulting from binding of O2 to the monolayer.