The use of perylenediimide (PDI) building blocks in materials for organic electronic is of considerable interest. The introduction of peripheral groups in their ortho and bay positions radically modify their optoelectronic properties. In this article, we describe an efficient method to afford regioisomerically pure 1,6/7-(NO2)2- and (NH2)2-PDIs employing two key steps: the selective crystallization of 1,6-(NO2)2-perylene-3,4,9,10-tetracarboxy tetrabutylester and the nitration of regiopure 1,7-Br2-PDI with silver nitrite. The optoelectronic properties of the resulting regioisomerically pure dinitro, diamino-PDIs and bisazacoronenediimides (BACDs) are reported and demonstrate the need to separate both regioisomers of such n-type organic semiconductors for their inclusion in advanced optoelectronic devices.
Two new macrocycles containing the bis(1,2,3-triazolyl)pyridine (btp) motif were prepared in high yields from a btp diazide precursor (1). Solution 1H NMR studies show that this diazide undergoes self–assembly with divalent transition metal ions to form ML2 complexes with pendant azide groups, apparently suitable for conversion into metal-templated catenanes; however attempts to form these catenanes were unsuccessful. Instead a new macrocycle containing two btp motifs was prepared, which forms a nanotube structure in the solid state. Reduction of the azide groups to amines followed by amide bond formation was used to convert 1 into macrocycle 8 containing btp and isophthalamide functionalities. This macrocycle binds halide and oxalate anions in acetonitrile solely through the isophthalamide motif, and binds aromatic dicarboxylates very strongly through both the isophthalamide amide donors and the btp triazole donors. The macrocycle was complexed with Pd(II) and the resulting complexes were shown to bind strongly to halide anions. The solid state structures of these [Pd·8·X]BF4 (X = Cl–, Br–, I–) were investigated by X-ray crystallography, which showed that [Pd·8·Br] forms an unusual “chain of dimers” structure assembled by metal complexation, N–H···Br– hydrogen bonding and short Pd···Pd contacts.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.