Vapor-Phase Living Assembly of π-Conjugated Organic Semiconductors

Abstract

In contrast to well-studied amphiphilic block copolymers (BCPs) and π-stacked dyes, living assembly of hydrophobic π-conjugated materials has not yet been explored to date. Using a microspacing physical vapor transport (PVT) technique, the prefabricated microrods of organic semiconductors involving 9,10-dicyanoanthracene (DCA, A) or its binary alloy (B) can act as seeds to initiate living homoepitaxial growth from their ends, giving elongated microrods with controlled length. Red-green-red tricolor fluorescent microrod heterostructures with low dispersity are further realized by living heteroepitaxial growth of B microrod blocks on A seed microrod tips. Upon varying the growth sequence of each block, reverse triblock microrods are also accessible. Such a seed-induced living growth is applicable to triblock microrod heterostructures of more binary combinations as well as even more complex penta- and hepta-block heterostructures comprising A and B. By virtue of a convenient vapor-phase growth method, the present work demonstrates the generality of living assembly of π-conjugated materials.

Vapor‐Phase Growth Strategies of Fabricating Organic Crystals for Optoelectronic Applications

“…In addition to the heterostructure of 1D microrods and 2D sheets, the organic multiblock heterostructure is valuable in the field of organic optoelectronics as well. [116][117][118] Lei et al [119] use the microspacing PVT technique to attain the self-assembly of hydrophobic π-conjugated molecules. Firstly, they combined the π-electron acceptor, 9,10-dicyanoanthracene (DCA, A), with the π-electron donor, perylene (Pe), in a certain ratio (0 < x ≤ 10%) through a coassembly pathway in solution to form a 1D binary charge transfer (CT) alloy combination (DCA 1-x Pe x , B) (Figure 12a).…”

“…[64,97] Ref. [115,119] b) The apparatus for vapor growth. c) The procedures of A microrods formation.…”

“…Reproduced with permission. [19,25,28,80,81,119,137] Copyright 2007, American Chemical Society. Copyright 2021, Wiley-VCH.…”

AIE-Active, Stimuli-Responsive Fluorescent 2D Block Copolymer Nanoplatelets Based on Corona Chain Compression

“…As a result of the analogy with living covalent polymerizations of organic monomers, living crystallization-driven self-assembly (CDSA) is of growing interest as a facile, ambient-temperature seeded growth route to colloidally stable 1D − and 2D ,− nanoparticles and more complex segmented and other hierarchical assemblies − with low dispersity and predetermined dimensions from crystallizable polymeric amphiphiles. The approach has also been expanded to π-stacking − and hydrogen-bonding amphiphilic molecular species in a process termed living supramolecular polymerization (LSP) , and also to vapor-phase approaches involving conjugated organic molecules . Beyond the formation of well-defined 1D and 2D nanostructures, both core- and corona-forming blocks can be modified to endow functionality to the assemblies prepared via living CDSA.…”

“…The approach has also been expanded to π-stacking 40−45 and hydrogen-bonding 46 amphiphilic molecular species in a process termed living supramolecular polymerization (LSP) 47,48 and also to vapor-phase approaches involving conjugated organic molecules. 49 Beyond the 54−56 and biomedical uses. 57−59 In this paper, we have explored the preparation and properties of AIE-active nanostructures based on BCPs with a crystallizable poly(ferrocenyldimethylsilane) (PFS) coreforming block, for which living CDSA is well established and where the electron-dense repeat units provide advantages for transmission electron microscopy (TEM) and scattering experiments.…”