Engineering Molecular Organization of Naphthalenediimides: Large Nanosheets with Metallic Conductivity and Attoliter Containers

Abstract

Molecular‐interaction‐induced organizations are the basis of various biological and nonbiological systems. The molecular recognition process involved in the formation of such systems is rather complicated, as it constitutes a subtle balance of various noncovalent interactions. The molecular organization of electron‐deficient aromatic systems is particularly appealing, as they are the potential candidates for a variety of applications. The main challenge in organizing aromatic moieties lies in controlling and optimizing the relatively strong π–π interactions by appropriate functionalization. Herein, we describe a simple molecular design involving phenylalanine methylester‐functionalized naphthalenediimide (L‐NDI and D‐NDI) to achieve high‐level molecular ordering by solution processing. NDIs are among the most promising organic n‐type semiconductors. However the molecular ordering of these organic entities determines their optimal functioning in an organic device. Highly crystalline free‐floating nanosheets with large lateral dimensions were obtained for the first time through molecularly engineered self‐assembly of L‐NDI and D‐NDI systems. Interestingly the nanosheets exhibit a remarkable conductivity of 1.6 S cm−1. Furthermore the molecular organization of L‐NDI was tuned into container‐like complex architectures by employing chlorinated‐ co‐solvent‐mediated halogen bonding. The composition and the type of chlorinated co‐solvent resulted in the formation of nanocups, mesocups, and bowl‐like architectures. The nanocups possess a net volume of 0.1–1.5 attoliters (10−18 L) and can be used as containers for miniaturized applications.

Molecular assembly of amino acid interlinked, topologically symmetric, π-complementary donor–acceptor–donor triads

“…The band at ~420 nm could be attributed to the aggregation band of NDI, while the band at ~550 nm is assigned to the charge-transfer complexation of NDI and pyrene. With further increase in the percentage of added water in DMSO, the amplitude of the CD signal approaches zero, suggesting a probable CD silencing [37]. Similar changes in the CD spectra were observed for 1 in aqueous NMP (Fig.…”

Large-size nanosheets of 9,10-bis(phenylethynyl)anthracene with high photoresponse and light emission anisotropy

“…[7][8][9] Highly organized large-size 2D nanostructures combine the feature of both thin films with the large lateral dimension and single crystals with the high-level molecule ordering, allowing the fabrication of competent devices with ease. 10 The 2D organic crystal system is an ideal system to study the optical and electronic properties. [10][11][12][13] However, compared to the extensive studies of 1D nanostructures, the investigations of large-size 2D The inset of (a) is the chemical structure of BPEA molecule.…”

“…10 The 2D organic crystal system is an ideal system to study the optical and electronic properties. [10][11][12][13] However, compared to the extensive studies of 1D nanostructures, the investigations of large-size 2D The inset of (a) is the chemical structure of BPEA molecule. The inset of (c) is an SEAD pattern recorded within a single nanosheet.…”

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

“…Although chirality is textbook concept in synthetic chemistry, few chiral organic semiconductors have been reported so far, in contrast of chiral conjugated polymers and chiral organic conductors that have received more attention . There are essentially two types of molecular structures, either the π‐systems are chiral and depart from planarity or chiral side‐groups are attached to a flat conjugated core .…”

“…The cause of such large contact resistance is not explained even if we can suspect that an inappropriate orientation of pentacene 1 molecules on top of the graphene electrodes. The consequence of such resistance is that the charge transport is injection limited as evidenced by the fact that the apparent mobility is channel length dependent . The fields of charge injection and contact engineering is particularly wide as different situations occur as a function of semiconductors, electrodes, and fabrication methods.…”