Heterochiral Doped Supramolecular Coordination Networks for High-Performance Optoelectronics

Abstract

Chiral self-sorting has great potential for constructing new complex structures and determining chirality-dependent properties in multicomponent mixtures. However, it is still of great challenge to achieve high fidelity chiral self-discrimination. Besides, the researches on the coordination polymers or metal−organic frameworks for micro/nanooptoelectronics are still rare due to their low conductivity and difficulty in developing a rapid and simple scale-up synthetic method. Here, heterochiral supramolecular coordination networks (SCNs) were synthesized by the solvothermal reaction of naphthalene diimide enantiomers and cadmium iodide, using the chirality as a synthetic tuning parameter to control the morphologies. Intriguingly, heterochiral micro/nanocrystals exhibited photochromic and photodetecting properties. Furthermore, we also developed a simple and efficient doping method to enhance the conductivity and photoresponsivity of micro/nanocrystals using hydrazine. From experimental and theoretical studies, the mechanism was suggested as follows: the radicals in the singly occupied molecular orbital level of the ligands provide charge carriers that can undergo "through-space" transport between π−π stacked ligands and the electron transfer from adsorbed hydrazine to the SCNs results in reduction of energy gap, leading to increased conductivity. Our findings demonstrate a simple and powerful strategy for implementing coordination networks with redox ligands for micro/nanooptoelectronic applications.

Preliminary chemical reduction for synthesizing a stable porous molecular conductor with neutral metal nodes

“…S4, ESI †) indicate that there is significant orbital overlap between the NDI-py molecules. Such an infinite p-stacked array of NDI cores in coordination polymers is still rare, 1,17,[32][33][34][35][36][37][38] even though vast numbers of coordination polymers with NDIbased ligands have been reported. 39,40 The LUMO level of NDI-py in PMC-2 was calculated to be À4.17 eV from the first reduction potential in the solid-state cyclic voltammogram (Fig.…”

Construction of naphthalene diimide-based cadmium complexes and their application in iodine adsorption, photochromism, and photocatalysis

“…The ligand AlaNDI was synthesized (Scheme S1 †) according to the literature. 65 Detailed structural characterization, special preparation methods of complexes 1 and 2, and the experimental procedures of photocatalytic dye degradation are given in the ESI. † Complexes 1 and 2 were prepared by the solvothermal reaction (Scheme S2 †).…”

“…29 It is making a great contribution to the low-carbon economy and the green energy network. However, many people are concerned about the safety of nuclear energy 30 and the management of nuclear waste. 31 Iodine is one of the radionuclides produced in nuclear waste and nuclear leakages.…”

“…[40][41][42][43][44][45][46][47][48] At present, there are many studies on naphthalimide (NDI) group complexes. [49][50][51][52][53][54] These complexes often have the advantages of the π-deficiency properties and give the π group (π⋯π stacking, anionic⋯π interaction, and CO⋯π interactions), forming a framework with less conventional weak noncovalent supramolecular interactions. 55 In addition, NDI derivatives with the auxiliary chromic groups can be easily grafted to fine-tune absorption and emission wavelengths.…”

Bay-Substitution Effect of Perylene Diimides on Supramolecular Chirality and Optoelectronic Properties of Their Self-Assembled Nanostructures

“…Chirality is ubiquitous in nature and can be observed in single molecules to entire galaxies. Among the hierarchical levels of chirality, supramolecular chirality has attracted a great deal of attention in the field of optoelectronics. − In particular, one-dimensional (1D) single-crystalline organic nanomaterials, which exhibit small physical dimensions, large surface area, and a defect-free nature, can be used to fabricate high-performance, miniaturized electronic, and optoelectronic devices. , Introducing chirality into such nanostructures can potentially lead to more advanced applications . However, applications involving chiral nanostructures, particularly those that incorporate chiral organic nanomaterials into optoelectronic devices, are in their infancy. ,, …”