Alkyl chain length regulated diverse 2D polymorphic self-assembly of benzothiadiazole-based π-conjugated fluorophore

Ke, Meixue; Ma, Tao; Wang, Yi; Zeng, Xiaofang; Miao, Xinrui; Cheng, Xiaonong; Deng, Wenli

doi:10.1016/j.apsusc.2022.153887

Cited by 9 publications

(7 citation statements)

References 39 publications

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“…Generally, the denser packing is expected at higher solute concentration due to the enthalpic reason . Conversely, the decreasing of the solution concentration may induce a structural transformation from higher packing densities to lower packing densities by changing the intermolecular bonding models. − At the same time, the entropy of the system also increases with the decrease in concentration. Furthermore, the characteristics of the solvent also play an important role in the formation ofa molecular assembly.…”

Section: Resultsmentioning

confidence: 99%

F···Br and F···S Heterohalogen-Bond-Directed 2D Self-Assemblies of a Benzothiadiazole Derivative

et al. 2023

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Halogen bonding (XB) is of great importance in fabricating a two-dimensional (2D) self-assembly for its adaptive directionality. However, the XBs involving fluorine (F) have barely been studied due to the absence of an σ-hole on F. Here, 2D selfassemblies of a F-substituted 4,7-bis(5-bromo-4-dodecylthiophen-2-yl)-5,6-difluorobenzo [c][1,2,5]thiadiazole (BTZ-BrF) molecule on graphite were investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. STM experiments revealed that the 2D patterns of BTZ-BrF had a clear solvent and concentration dependence, showing a frame-like pattern in aliphatic acid and aliphatic hydrocarbon solvents at high concentrations. At lower concentrations, a bamboo-like and a wave-like pattern were observed in aliphatic acid, whereas small frame-like and large ladder-like domains at high solution concentrations in aliphatic hydrocarbon were observed. As the concentration further decreased, two linear patterns were observed. DFT calculations suggested that the hetero-XBs of Fand Br•••N, the homo-XBs of type-II Br•••Br, and the S•••S interactions synergistically directed and stabilized the polymorphic 2D architectures. This understanding of intermolecular XBs during the molecular assembly at the molecular level may shed light on the ongoing efforts of regulating nanostructures of multifunctional organics.

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Section: Resultsmentioning

confidence: 99%

F···Br and F···S Heterohalogen-Bond-Directed 2D Self-Assemblies of a Benzothiadiazole Derivative

et al. 2023

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“…Controlling two-dimensional self-assembled supramolecular nanostructures on surfaces has received a great deal of attention for purely theoretical research reasons as well as applications in nanotechnology and crystal engineering. − Particularly, the well-ordered nanoporous networks, such as rhombus, Kagomé, and honeycomb, constructed by intermolecular noncovalent interactions are extensively used as host templates to immobilize and recognize functional guest molecules. − With this view, a broad range of host template structures could be obtained by adopting various geometries and functionalities of molecular building blocks. − Utilizing the so-called host–guest assembly method, the functionality and complexity of interfacial architectures can be expanded significantly. − The coadsorption of guest molecules may maximize the host–guest interactions and the van der Waals (vdW) interactions between the adsorbates and substrates to stabilize the coassembly system. − In most cases, the incorporation of guest molecules with appropriate size into the host template does not result in any movement of the host matrix. − Besides, the host molecule could adaptively reorganize 2D nanoporous networks more flexibly via the breakage and generation of noncovalent bonds induced by guest species. − Thus, it is frequently proposed that the size and shape complement of the host porous template and guest molecules play a key role in responding to guest inclusion assembly. , …”

Section: Introductionmentioning

confidence: 99%

Fabricating 2D Host −Guest Kagomé Packing for C₂-Symmetric Aromatic Carboxylic Acids with Different Spatial Configuration: Different Ways, Same Destination

et al. 2023

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The self-assembly of two kinds of C2-symmetric aromatic carboxylic acids named 4,4′,4″,4‴-(1,4-phenylenebis(azanetriyl))tetrabenzoic acid (H4PTA) and 5′,5″-bis(4-carboxyphenyl)-[1,1′:3′,1″:3″,1‴-quaterphenyl]-4,4‴-dicarboxylic acid (H4QDA) and the coadsorption with coronene (COR) molecules at different solution concentrations were investigated at the heptanoic acid (HA)/highly oriented pyrolytic graphite (HOPG) interface by scanning tunneling microscopy (STM). H4PTA molecules with nonplanar conformation self-assembled into a highly ordered rhombus structure at variational concentrations and subsequently could be regulated into a Kagomé network by the coadsorption of COR molecules. H4QDA molecules with planar conformation self-assembled into two various nanostructures (rhombus structure and Kagomé network) coexisting on the HOPG surface at different concentrations. The Kagomé architecture of H4QDA could act as a rigid host template to trap the COR molecules. Meanwhile, COR exhibited preferential adsorption in the porous template: COR only entered the hexagonal cavities at low concentrations and filled in all hexagonal and triangular cavities at high concentrations. Density functional theory (DFT) calculations and molecular dynamics (MD) simulations showed that the host–guest co-assembled structures were more thermodynamically and kinetically stable. The formation of different self-assembly and co-assembly processes of two molecules could be attributed to the dissimilar molecular conformation. Our work is of significance to further explore the formation mechanism of two-dimensional (2D) porous arrangements and provides an ideal way to regulate the adsorption of porous templates.

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“…[38][39][40] In addition, the host network constructed by van der Waals forces between alkyl chains has attracted researchers' attention due to its self-assembly diversity and flexible self-regulation ability. [41][42][43] Moreover, scanning tunneling microscopy (STM) is a powerful detective method for realtime, in situ, and accurate exploration of complex assembly structures at interfaces. 44 In this paper, two kinds of carboxylic acid molecules containing three pairs of meta-carboxyl groups, namely H 6 PDB and H 6 PAB (Fig.…”

Section: Introductionmentioning

confidence: 99%

Coronene guest molecule selectivity in host templates formed by hydrogen bonding and van der Waals forces at liquid/solid interfaces

et al. 2023

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Alkyl chain length regulated diverse 2D polymorphic self-assembly of benzothiadiazole-based π-conjugated fluorophore

Cited by 9 publications

References 39 publications

F···Br and F···S Heterohalogen-Bond-Directed 2D Self-Assemblies of a Benzothiadiazole Derivative

F···Br and F···S Heterohalogen-Bond-Directed 2D Self-Assemblies of a Benzothiadiazole Derivative

Fabricating 2D Host −Guest Kagomé Packing for C₂-Symmetric Aromatic Carboxylic Acids with Different Spatial Configuration: Different Ways, Same Destination

Coronene guest molecule selectivity in host templates formed by hydrogen bonding and van der Waals forces at liquid/solid interfaces

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Alkyl chain length regulated diverse 2D polymorphic self-assembly of benzothiadiazole-based π-conjugated fluorophore

Cited by 9 publications

References 39 publications

F···Br and F···S Heterohalogen-Bond-Directed 2D Self-Assemblies of a Benzothiadiazole Derivative

F···Br and F···S Heterohalogen-Bond-Directed 2D Self-Assemblies of a Benzothiadiazole Derivative

Fabricating 2D Host −Guest Kagomé Packing for C2-Symmetric Aromatic Carboxylic Acids with Different Spatial Configuration: Different Ways, Same Destination

Coronene guest molecule selectivity in host templates formed by hydrogen bonding and van der Waals forces at liquid/solid interfaces

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Fabricating 2D Host −Guest Kagomé Packing for C₂-Symmetric Aromatic Carboxylic Acids with Different Spatial Configuration: Different Ways, Same Destination