DNA-Templated Assembly of Naphthalenediimide Arrays

π‐Stacked naphthalenediimide (NDI) arrays are of interest as charge‐transport materials. We have designed and synthesized an NDI derivative with two ZnII–cyclens that act as receptors for the thymine base in DNA. UV/Vis and CD spectroscopy, gel filtration, and molecular‐modeling studies have shown that the bis(ZnII–cyclen)–NDI can be assembled in the presence of oligo‐dT to form π‐stacked NDI arrays. The assembly of the NDI arrays was found to be dependent on the length of the oligo‐dT and the temperature. The NDI–oligo‐dT assembly on a gold substrate exhibits photocurrent responses due to electron transfer through the π‐stacked array. It stacks up: A naphthalenediimide (NDI) derivative (1) with two ZnII–cyclens that act as receptors for the thymine base in DNA has been synthesized. UV/Vis and CD spectroscopy, gel filtration, and molecular‐modeling studies have shown that the bis(ZnII–cyclen)–NDI can be assembled in the presence of oligo‐dT to form π‐stacked NDI arrays (see scheme).