Molecular Architectonics of Naphthalenediimides for Efficient Structure–Property Correlation

Abstract

We present a bioinspired design strategy to effectively tailor the assembly of naphthalenediimides (NDIs) into a wide variety of architectures by functionalizing with amino acid derivatives. This bioinspired process of custom designing and engineering molecular assemblies is termed "bioinspired architectonics". By employing minute structural mutations in the form of α-substituents of amino acids, we successfully engineered molecular assembly of NDIs into zero-dimensional (0D, spheres), one-dimensional (1D, fibers), and two-dimensional (2D, sheets) architectures. The 2D sheets of phenylalanine methylester appended NDI 1 showed remarkable bulk electron mobility of up to 1 cm(2) V(-1)s(-1). With the aid of photophysical, diffraction, and microscopy techniques we rationalize the effect of molecular structure with their ordering and electronic properties in an effort to find structure-property correlations via a bioinspired modular approach.

A Dynamic View of Proton-Coupled Electron Transfer in Photocatalytic Water Splitting

“…The potential problem of charge recombination can be also alleviated by inserting appropriate molecular bridge units with rectifying properties between the dye and the semiconductor 16,59,80,81 or by engineering n/p-supramolecular heterojunctions. [45][46][47][48] We will no further address this point in this work and assume a long-lived oxidized state.…”

“…44 Furthermore, they allow the construction of n/p-supramolecular heterojunctions presenting antiparallel gradients in electron and holes channels to achieve photoinduced long-distance charge separation and reduce charge recombination. [45][46][47][48] Scheme 1. Schematic representation of the proposed photoanode (1) including the acceptorsemiconductor (TiO 2 ), the molecular chromophore NDI 1 , and the Ru-based water oxidation catalyst; (1a) chromophore-semiconductor subsystem employed for the photoinduced electron injection simulation; (1b) chromophore-catalyst subsystem used in the simulation of the first water oxidation catalytic step.…”

Homochiral Asymmetric‐Shaped Electron‐Transporting Materials for Efficient Non‐Fullerene Perovskite Solar Cells

“…This homochirality of two PhE groups at each end of the NDI core decreases the molecular symmetry of NDI‐PhE. Although introducing chiral groups onto π‐conjugated semiconducting cores has been reported previously, most studies have been focused on the chiroptical activity and formation of supramolecular nanostructures, rather than on the effect on solubility or solution processability with good film‐forming ability for electronic devices . The homochiral NDI‐PhE is synthesized by a condensation reaction between the chiral reagent ( R )‐1‐phenylethanamine and the achiral 1,4,5,8‐naphthalenetetracarboxylic dianhydride .…”

“…Although introducing chiral groups onto p-conjugated semiconducting cores has been reportedp reviously,m ost studies have been focused on the chiroptical activity and formationo fs upramolecular nanostructures, rather than on the effect on solubility or solution processability with good film-forminga bility for electronic devices. [43][44][45][46][47] The homochiral NDI-PhE is synthesized by ac ondensation reaction between the chiral reagent (R)-1-phenylethanamine andt he achiral 1,4,5,8-naphthalenetetracarboxylic dianhydride. [46,47] It can be expected that reduced molecular symmetry and increased free volumei ntroducedb yh omochiral asymmetric-shaped PhE groups enhance solubility and film-forming ability for electronic devices such as PSCs.…”

Molecular Architectonics‐Guided Fabrication of Superhydrophobic and Self‐Cleaning Materials

“…[ 30–37 ] Molecular architectonics facilitates the creation of functional micro/nanoarchitectures through the meticulously planned organization of suitably designed functional molecular building blocks through the bottom–up approach from the molecular level. [ 30,31,38–41 ] However, we must note that the uncontrolled or unspecific aggregation or crystallization of small molecules are unable to either roll off or stabilize the water droplets. In this context, the principles of molecular architectonics guide the ordered assembly of functional small molecules in a defined shape, size, and pattern to construct material surfaces with required roughness and low‐surface energy to render them with superhydrophobicity and possibly self‐cleaning property.…”