Constitution and Conductivity of Metalloporphyrin Tapes

Metalloporphyrin tapes form in a solvent‐free oxidative chemical vapor deposition process on glass substrates. The metal center (M = NiII, CuII, ZnII, CoII, PdII, FeIIICl, 2H) in the 5,15‐disubstituted porphyrin monomer affects the initial C–C coupling step and consequently the formation of triply or doubly linked porphyrin tapes as well as the interchain interaction in the tape as shown by optical spectroscopy, high resolution mass spectrometry and X‐ray photoelectron spectroscopy. Optical spectroscopy and conductive atomic force microscopy reveal that these factors influence the near‐infrared absorbance and the electrical conductivity of the films. Consequently, the metal ion of the metalloporphyrin allows tuning of the macroscopic properties of the thin films composed of metalloporphyrin tapes. Porphyrin tapes: Oxidative chemical vapor deposition of 5,15‐disubstituted metalloporphyrins gives metalloporphyrin tapes (M = 2H, FeIIICl, CoII, NiII, CuII, ZnII, PdII) in a single step. The metal center steers the regioselectivity of the initial C–C coupling reaction. The resulting double or triple linkages determine the NIR absorbance and conductivity of the resulting thin films.