RESUMEN
Supramolecular coordination self-assembly on solid surfaces provides an effective route to form two-dimensional (2D) metal-organic frameworks (MOFs). In such processes, surface-adsorbate interaction plays a key role in determining the MOFs' structural and chemical properties. Here, we conduct a systematic study of Cu-HAT (HAT = 1,4,5,8,9,12-hexaazatriphenylene) 2D conjugated MOFs (c-MOFs) self-assembled on Cu(111), Au(111), Ag(111), and MoS2 substrates. Using scanning tunneling microscopy and density functional theory calculations, we found that the as-formed Cu3HAT2 c-MOFs on the four substrates exhibit distinctive structural features including lattice constant and molecular conformation. The structural variations can be attributed to the differentiated substrate effects on the 2D c-MOFs, including adsorption energy, lattice commensurability, and surface reactivity. Specifically, the framework grown on MoS2 is nearly identical to its free-standing counterpart. This suggests that the 2D van der Waals (vdW) materials are good candidate substrates for building intrinsic 2D MOFs, which hold promise for next-generation electronic devices.
RESUMEN
The experimental realization of p-orbital systems is desirable because p-orbital lattices have been proposed theoretically to host strongly correlated electrons that exhibit exotic quantum phases. Here, we synthesize a two-dimensional Fe-coordinated bimolecular metal-organic framework which constitutes a honeycomb lattice of 1,4,5,8,9,12-hexaazatriphenylene molecules and a Kagome lattice of 5,15-di(4-pyridyl)-10,20-diphenylporphyrin molecules on a Au(111) substrate. Density-functional theory calculations show that the framework features multiple well-separated spin-polarized Kagome bands, namely Dirac cone bands and Chern flat bands, near the Fermi level. Using tight-binding modelling, we reveal that these bands are originated from two effects: the low-lying molecular orbitals that exhibit p-orbital characteristics and the honeycomb-Kagome lattice. This study demonstrates that p-orbital Kagome bands can be realized in metal-organic frameworks by using molecules with molecular orbitals of p-orbital like symmetry.
RESUMEN
1,4,5,8,9,12-Hexaazatriphenylene (HAT) is one of the smallest polyheterocyclic aromatic building blocks for forming conjugated metal-organic frameworks (cMOFs). However, the strong inter-molecular steric hindrance impedes the growth of HAT-based cMOFs. Here we employ on-surface synthesis to grow single-layer two-dimensional cMOFs of M3 (HAT)2 (M=Ni, Fe, Co). Using scanning tunnelling microscopy and density-functional theory (DFT) analysis, we resolve that the frameworks comprise a hexagonal lattice of HAT molecules and a Kagome lattice of metal atoms. The DFT analysis indicates that Ni, Co and Fe carry a magnetic moment of 1.1, 2.5, and 3.7â µB, respectively. We anticipate that the small π-conjugated core of HAT and strong bidentate chelating coordination give rise to appealing electronic and magnetic properties.
RESUMEN
Creating conjugated macrocycles has attracted extensive research interest because their unique chemical and physical properties, such as conformational flexibility, intrinsic inner cavities and aromaticity/antiaromaticity, make these systems appealing building blocks for functional supramolecular materials. Here, we report the synthesis of four-, six- and eight-membered tetraphenylethylene (TPE)-based macrocycles on Ag(111) via on-surface Ullmann coupling reactions. The as-synthesized macrocycles are spontaneously segregated on the surface and self-assemble as large-area two-dimensional mono-component supramolecular crystals, as characterized by scanning tunneling microscopy (STM). We propose that the synthesis benefits from the conformational flexibility of the TPE backbone in distinctive multi-step reaction pathways. This study opens up opportunities for exploring the photophysical properties of TPE-based macrocycles.
RESUMEN
In this paper, we report on the ultrafast laser-induced birefringence, refractive index changes, and enhanced photoluminescence properties in the volume of neodymium (Nd), yttrium (Y) co-doped strontium fluoride (SrF2) and Nd, Y co-doped calcium fluoride (CaF2) crystals. The optical waveguides written with 500 kHz repetition rate provided lowest propagation loss of 1.63±0.21 dB cm-1 for transverse magnetic (TM) polarization at 632.8 nm in Nd,Y:SrF2 crystal. The measured retardance can be interpreted by stress-induced birefringence related to the permanent volume expansion, photo induced by a non-spherical irradiated zone. The absorption, steady-state, and time-resolved photoluminescence properties are also carried out in and out of the laser irradiated zone, enabling the local changes of the Nd and Y network in Nd,Y:SrF2, as well as well-preserved Nd fluorescence in the written optical waveguides.
RESUMEN
Novel functionalized graphene oxide π-π stacking with conjugated polymers (P-GO) is fabricated via a simple ethanol-mediated mixing method, leading to better dispersion in organic nonpolar solvents and bypassing the inherent restrictions of hydrophilicity and oleophobicity. We analyze the mechanism of the incorporation of P-GO into inverted organic solar cells (OSCs) based on a poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4- b]thiophenediyl]] (PTB7):[6,6]-phenyl C71 butyric acid methyl ester (PC71BM) system to investigate the possibility of high-performance thick-film OSC fabrication. It is verified that the incorporation of P-GO into the PTB7:PC71BM blend films leads to a decreased π-π stacking distance, enlarged coherence length for polymer, and optimized phase separation, resulting in more effective charge dissociation, reduced bimolecular recombination, and more balanced charge transport. The OSCs with 1% P-GO incorporation demonstrate a thickness-insensitive fill factor (57.8%) and power conversion efficiency (PCE) (7.31%) even with 250 nm thick photoactive layers, leading to a dramatic PCE enhancement of 34% compared with the control devices with the same thickness.