Photoelectrochemical Effects and (Photo)Conductivity of “N-Type” Phthalocyanines

Structural and Electronic Effects Due to Fluorine Atoms on Dibenzotetraaza-Annulenes Complexes

“…Similar effects on the electron density distribution were reported for phthalocyanine complexes for which the substitution with electron-withdrawing groups causes a decrease of electron density in the inner ring π-system and may induce the switching from p-type to n-type semiconductor behavior. 14 As expected, these findings are in agreement with the observed intermolecular interactions and confirm the role played by the fluorine atoms in the crystal structures of these compounds. Indeed, in 1F , the fluorine atoms (negative EP) show short contacts with H and C at the benzene rings (positive EP), whereas the unsubstituted complex presents interactions involving hydrogen atoms and the partially negatively charged aromatic carbons.…”

“…7−14 The addition of benzene rings to the phthalocyanine, for instance, causes a red-shift of the intense absorption at the longest wavelength, 8 whereas a switch from p-type to air-stable n-type semiconductor behavior occurs when the peripheral hydrogen atoms are substituted with fluorines. 9,10,14 The exchange of a part or all of the C–H bonds with C–F ones at the outer rim of the macrocyclic ligands also heavily affects the ambient stability of the complexes, 9,10 as well as their catalytic 15−17 and therapeutic properties. 18 Moreover, the presence of fluorine atoms also changes the surface tension, the thermal stability, 11 and the solubility of the molecules.…”

Organic Thin Film Transistors for Large Area Electronics

“…[136] For example, the work of Bao et al explored a variety of metallophthalocyanines as channels in n-type OTFTs. [137] Chemical functionality, substrate temperature during the deposition as well as the metal center used were all critical to device performance.…”

“…Although historically, metallophthalocyanines have been examined as p-type, [135] appropriate substitution can allow for the fine tuning of the HOMO±LUMO levels thus altering the majority charge carrier of the material. [136] For example, the work of Bao et al explored a variety of metallophthalocyanines as channels in n-type OTFTs. [137] Chemical functionality, substrate temperature during the deposition as well as the metal center used were all critical to device performance.…”

Electrodeposited Porous ZnO Sensitized by Organic Dyes – Promising Materials for Dye‐Sensitized Solar Cells with Potential Application in Large‐Scale Photovoltaics

“…This was shown for (CN) 8 PcZn [140,205] , TPyTAPZn [140, 206,207] , and TPzTAPZn [140,206] . Based on these results, n -type conductivity was assigned to these materials of molecules with electron -withdrawing substituents based on the argument outlined above [129, 140, 205 -209] .…”