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In crystals, tetraalkyl vanadyl phthalocyanines (OVPc‐Cn) and tetraalkyl titanyl phthalocyanines (OTiPc‐Cn) with ABAB symmetry adopt a 2D slipped π–π stacking motif with alkyl chains locating in the space between semiconducting layers formed by Pc cores. Hole mobility approaching 1 cm2 V−1 s−1 is achieved for spin cast OFETs.
Four structural isomers of non‐peripheral tetrahexyl‐substituted vanadyl phthalocyanine can be easily separated using common laboratory column chromatography on a gram scale. The most abundant isomer, 1,8,18,22‐tetrahexyl vanadyl phthalocyanine (I‐3), adopts intermolecular 2D cofacial π–π stacking and exhibits a field‐effect mobility of up to 0.13 cm2 V−1 s−1.
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