Porphyrins and related families of molecules are important organic modules as has been reflected in the award of the Nobel Prizes in Chemistry in 1915, 1930, 1961, 1962, 1965, and 1988 for work on porphyrin-related biological functionalities. The porphyrin core can be synthetically modified by introduction of various functional groups and other elements, allowing creation of numerous types of porphyrin derivatives. This feature makes porphyrins extremely useful molecules especially in combination with their other interesting photonic, electronic and magnetic properties, which in turn is reflected in their diverse signal input–output functionalities based on interactions with other molecules and external stimuli. Therefore, porphyrins and related macrocycles play a preeminent role in sensing applications involving chromophores. In this review, we discuss recent developments in porphyrin-based sensing applications in conjunction with the new advanced concept of nanoarchitectonics, which creates functional nanostructures based on a profound understanding of mutual interactions between the individual nanostructures and their arbitrary arrangements. Following a brief explanation of the basics of porphyrin chemistry and physics, recent examples in the corresponding fields are discussed according to a classification based on physical modes of detection including optical detection (absorption/photoluminescence spectroscopy and energy and electron transfer processes), other spectral modes (circular dichroism, plasmon and nuclear magnetic resonance), electronic and electrochemical modes, and other sensing modes.

Both the reversible trans ↔ cis photoisomerization and slow thermal back cis-to-trans isomerization of azobenzene-functionalized self-assembled monolayers on gold surfaces have been achieved by rationally designed single-component azobenzene thiol.

We report the successful fabrication of azobenzene-functionalized self-assembled monolayers (SAMs) exhibiting high and reversible photoswitching between trans and cis states on a flat gold surface. Azobenzene thiols (MeSH and EtSH) containing meta and/or ortho substituents were chosen based on the occupied area per molecule as well as intermolecular interactions between the azobenzene aromatic rings (formation of H-aggregates). Theoretical predictions of the geometrical structures were performed to clarify the correlation between the molecular structure and photoisomerization characteristics in monolayer systems. The striking difference in absorption spectra of a trans-EtSH SAM and a cis-EtSH SAM by alternating UV and visible light irradiation was in good agreement with that in their contact angles for water, strongly indicating that the structural changes were controlled by light wavelength. By contrast, despite there being sufficient free space for each MeSH molecule, the strong tendency of the planar azobenzene units to generate H-aggregates even during cis-MeSH SAM formation lessened the trans-to-cisphotoisomerization yield in a monolayer.