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(Metallo)porphyrins for potential materials science applications
The bottom-up approach to replace existing devices by molecular-based systems is a subject that attracts permanently increasing interest. Molecular-based devices offer not only to miniaturize the device further, but also to benefit from advanced functionalities of deposited molecules. Furthermore, the molecules itself can be tailored to allow via their self-assembly the potential fabrication of devices with an application potential, which is still unforeseeable at this time. Herein, we review efforts to use discrete (metallo)porphyrins for the formation of (sub)monolayers by surface-confined polymerization, of monolayers formed by supramolecular recognition and of thin films formed by sublimation techniques. Selected physical properties of these systems are reported as well. The application potential of those ensembles of (metallo)porphyrins in materials science is discussed.
Synthesis, spectroscopic characterization and thermogravimetric analysis of two series of substituted (metallo)tetraphenylporphyrins
Subsequent treatment of H2TPP(CO2H)4 (tetra(p-carboxylic acid phenyl)porphyrin, 1) with an excess of oxalyl chloride and HNR2 afforded H2TPP(C(O)NR2)4 (R = Me, 2; iPr, 3) with yields exceeding 80%. The porphyrins 2 and 3 could be converted to the corresponding metalloporphyrins MTPP(C(O)NR2)4 (R = Me/iPr for M = Zn (2a, 3a); Cu (2b, 3b); Ni (2c, 3c); Co (2d, 3d)) by the addition of 3 equiv of anhydrous MCl2 (M = Zn, Cu, Ni, Co) to dimethylformamide solutions of 2 and 3 at elevated temperatures. Metalloporphyrins 2a–d and 3a–d were obtained in yields exceeding 60% and have been, as well as 2 and 3, characterized by elemental analysis, electrospray ionization mass spectrometry (ESIMS) and IR and UV–vis spectroscopy. Porphyrins 2, 2a–d and 3, 3a–d are not suitable for organic molecular beam deposition (OMBD), which is attributed to their comparatively low thermal stability as determined by thermogravimetric analysis (TG) of selected representatives.