Abstract
Skewered Iron(III) phthalocyanine conducting polymer can be constructed with the utilization of axial thiocyanato ligands ((μ-thiocyanato)(phthalocyaninato)iron(III)); (FeIII(Pc)(SCN)n) thereby creating additional avenues for electron transport through a linear SCN bridge, apart from the intermolecularπ-πorbital overlap between the Pc molecules. In this paper, we report on the conversion of bulkFeIII(Pc)(SCN)npolymeric organic conductor into crystalline nanostructures through horizontal vapor phase growth process. The needle-like nanostructures are deemed to provide more ordered and, thus, moreπ-πinteractive interskewerFeIII(Pc)(SCN)npolymer orientation, resulting in a twofold increase of its electrical conductivity per materials density unit.
Highlights
Phthalocyanines (Pc; Scheme 1) with metal centers (MPc) are considered to be one of the most promising organic conductors because of its flat and fully conjugated structure that provides facile intramolecular π-electron delocalization
The electrical conduction of slip-stacked MPc units highly depends on its arrangement in solid-state which is mainly due to the effectiveness of its intermolecular π-π orbital overlap/interaction (Scheme 2(a)) [6, 7], while the polymerization of MPcL2 through axialligand bridge extends the highly delocalized πelectron of the macrocycle by forming linear π-electron containing organic molecules, resulting in additional stacking dimension for the π-electron transport, and thereby minimizing dependence on solid-state orientation (Scheme 2(b)) [8]
We explore on the possibility of further increasing the electrical conductivity of the [FeIII(Pc)(SCN)]n polymeric system through its conversion into nanostructures
Summary
Phthalocyanines (Pc; Scheme 1) with metal centers (MPc) are considered to be one of the most promising organic conductors because of its flat and fully conjugated structure that provides facile intramolecular π-electron delocalization. The resulting nanostructured [FeIII(Pc)(SCN)]n provide multidimensional π-electron transport in the Pc molecule by adopting the enforced tetragonal packing that further increases the stacking dimensionality by producing intra- and inter- (skewer) π-orbital interactions (Scheme 3), the higher electrical conductivity. This technique may serve as a facile and convenient method for increasing the conductivity of organic polymers with similar linear architectures, for which it may be considered as a promising class of molecular conductor
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