Halogen Bonds Fabricate 2D Molecular Self-Assembled Nanostructures by Scanning Tunneling Microscopy

Wang, Yi; Miao, Xinrui; Deng, Wenli

doi:10.3390/cryst10111057

Cited by 17 publications

(12 citation statements)

References 91 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the case of contacts Cg3(C16 ÷ C21)…Br4 and Cg4(C23 ÷ C28)…Br4, the bromine atom is closer to the centers of aromatic rings, which are electron-deficient regions. The aforesaid provides one more example of the unique ability of the bromine substituents to interact with both nucleophilic and electrophilic centers, which has gained great attention in the last decade [ 38 ].…”

Section: Resultsmentioning

confidence: 99%

Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb3-Luminescence via Upper-Rim Substitution+

et al. 2022

View full text Add to dashboard Cite

The present work introduces the series of thiacalix[4]arenes (H4L) bearing different upper-rim substituents (R = H, Br, NO2) for rational design of ligands providing an antenna-effect on the NIR Yb3+-centered luminescence of their Yb3+ complexes. The unusual inclusive self-assembly of H3L− (Br) through Brπ interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb3+:2HL3−] leads to efficient sensitizing of the Yb3+ luminescence for H4L (Br, NO2), while poor sensitizing is observed for ligand H4L (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl3 and H4L(NO2) has revealed the transformation of the dimeric complexes into [4Yb3+:2L4−] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of H4L(R = NO2), where the triplet level at 567 nm (17,637 cm−1) arisen from ILCT provides efficient sensitizing of the Yb3+ luminescence.

show abstract

Section: Resultsmentioning

confidence: 99%

Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb3-Luminescence via Upper-Rim Substitution+

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Halogen bonds have a broad and significant impact in various areas . They play a crucial role in the design and fabrication of supramolecular structures, including self-assembled molecular architectures, host–guest complexes, and nanostructures . Furthermore, they contribute to the formation and stabilization of crystal structures and are employed in biology and biochemistry to enhance molecular recognition and binding affinity .…”

Section: Introductionmentioning

confidence: 99%

Exploring C–F···π Interactions: Synthesis, Characterization, and Surface Analysis of Copper β-Diketone Complexes

Mirtamizdoust,

Karamad,

Mojtabazade

et al. 2024

ACS Omega

View full text Add to dashboard Cite

Synthesis and characterization of two novel copper β-diketone complexes, where halogen bonds play a pivotal role in shaping their multifaceted structural landscape, have been done in the present study. This study employs Xray diffraction, ultraviolet−visible (UV−vis) spectroscopy, and infrared (IR) spectroscopy to investigate two copper β-diketone complexes, [Cu(L1) 2 (ttfa) 2 ]• 2CH 3 OH (1) and [Cu(L1)(dfpb) 2 ] (2), where Httfa is 4,4,4-trifluoro-1-(thiophen-2-yl)butan-3,1-dione and Hdfpb is 4,4-difluoro-1-phenylbutane-1,3dione. Complex 1 displays a halogen bond, which contributes to its uniqueness. The coordination sphere around the copper atoms was found to be octahedral for complex 1 and pyramid with a square base for complex 2. The study also extensively discusses the interactions present in these complexes. Hirshfeld surface analysis was employed to gain a more detailed understanding of these interactions, and the results showed that hydrogen-bond interactions contributed above 30% of the whole surface area in both complexes. Additionally, the halogen bond in complex 1 was found to contribute approximately 8% of the surface. Overall, this study provides valuable insights into the structural properties and interactions of copper β-diketone complexes, which could have potential applications in various fields. ■ HIGHLIGHTS• Diverse coordination geometries found in the copper βdiketone complexes. • Comprehensive analysis of the interactions within the complexes.• Hirshfeld surface analysis employed to gain a detailed understanding of complex interactions. • Halogen bond observed in one of the copper β-diketone complexes. • Hydrogen-bond interactions contribute significantly to the surface in the complexes.

show abstract

“…Despite the prosperous studies of XBs, the 2D assembly directed by the halogen synthons involving fluorine (F) is rarely seen since F usually shows low polarizability with no σ-hole. ,, To explore the F···F interaction, Kawai et al compared the 2D self-assemblies of nonsubstituted phenyleneethynylene (BPEPE) and fully fluoro-substituted phenyleneethynylene (BPEPE-F18) on the Ag(111) surface at low temperature . The ab initio calculation revealed that the anisotropic distribution of electrostatic potential will occur around fluorine, thus leading to the formation of a “windmill” structure via highly directional bonding on the surface, which was very much like the XBs even though there was no σ-hole at the F ends.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2023

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Halogen Bonds Fabricate 2D Molecular Self-Assembled Nanostructures by Scanning Tunneling Microscopy

Cited by 17 publications

References 91 publications

Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb3-Luminescence via Upper-Rim Substitution+

Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb3-Luminescence via Upper-Rim Substitution+

Exploring C–F···π Interactions: Synthesis, Characterization, and Surface Analysis of Copper β-Diketone Complexes

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

Contact Info

Product

Resources

About