Computational Design of 3D Lantern Organic Framework DOI Open Access
Lam Nguyen, Thanh N. Truong

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(61)

Published: Aug. 22, 2024

Abstract This study employed a computational approach, particularly Density Functional Theory at B3LYP−D3/6‐31+G(d) level to design two new classes of three‐dimensional (3D) Lantern Organic Frameworks (LOFs) materials based on trisilasumanene and porphyrin core building units. Particularly, we detail strategies for transitioning from 1D‐LOF nanowires extended 3D structures: first by connecting planar‐molecule base units or using benzene‐based linkers, then silicon anchoring atoms the bases with other that are vertically stacked sp 3 ‐hydrocarbon chains. The 3D‐LOF structures designed have different pore sizes through use various bases, bridges, linkers. Comparisons electronic properties these lead one designing rule. That is, gap between highest occupied molecular orbital (HOMO) lowest unoccupied (LUMO) depends only its is nearly independent stack size length bridges. Additionally, linkers also extends π‐electron conjugation system leading reduction in HOMO‐LUMO gap. For instance, linking molecules significantly narrows 1.75 eV while stacking them linear pentane‐based bridges yield insignificant change

Language: Английский

Advances and challenges in the electrochemical reduction of carbon dioxide DOI Creative Commons

Jingyi Han,

Xue Bai,

Xiaoqin Xu

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(21), P. 7870 - 7907

Published: Jan. 1, 2024

This review highlights the structure–activity relationship of ECO 2 RR, provides a detailed summary advanced materials by analyzing electrocatalytic applications and reaction mechanisms, discusses challenges in both devices.

Language: Английский

Citations

49
Phthalocyanine Covalent Organic Frameworks: Dimensionality Effect on Third‐Order Nonlinear Optical Properties DOI
Bin Han, Bin Liang, Enhui Zhang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: April 8, 2024

Abstract Dimensionality of covalent organic frameworks (COFs), in terms 2D and 3D, must greatly influence their properties functionalities due to the different electronic porous structures, but still less investigated 20 years history. Herein, on basis imidization reaction phthalocyanine‐based tetraanhydride monomers with either 1,4‐phenylenediamine or 1,3,5,7‐tetra(4‐aminophenyl)adamantine, 3D imide‐bonded COFs sql pts topology have been prepared explore third‐order nonlinear optical (NLO) properties. In contrast metal‐free analogues, both copper‐phthalocyanine enhanced NLO behaviors according open aperture Z‐scan limiting (OL) results recorded under a nanosecond laser at 532 nm. particular, strong π – staking phthalocyanine units show property bigger susceptibility ( Imχ (3) ) unique reverse saturation absorption response 1064 nm than that species dispersed conjugated modules. Furthermore, femtosecond transient spectra disclose longer excited lifetimes copper metal free samples, helpful property. These findings clearly materials advantages toward characteristics provide new candidates for OL application.

Language: Английский

Citations

11
Two-Dimensional Organic–Inorganic van der Waals Hybrids DOI

Fucai Cui,

Víctor García‐López, Zhiyong Wang

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

Two-dimensional organic-inorganic (2DOI) van der Waals hybrids (vdWhs) have emerged as a groundbreaking subclass of layer-stacked (opto-)electronic materials. The development 2DOI-vdWhs via systematically integrating inorganic 2D layers with organic crystals at the molecular/atomic scale extends capabilities traditional vdWhs, thanks to their high synthetic flexibility and structural tunability. Constructing an hybrid interface atomic precision will unlock new opportunities for generating unique interfacial transport properties by combining strengths layers, thus allowing us satisfy growing demand multifunctional applications. Here, this review provides comprehensive overview latest advancements in chemical synthesis, characterization, numerous applications 2DOI-vdWhs. Firstly, we introduce chemistry physical recently rising (O2DCs), which feature crystalline nanostructures comprising carbon-rich repeated units linked covalent/noncovalent bonds exhibit strong in-plane extended π-conjugation weak interlayer vdWs interaction. Simultaneously, representative (I2DCs) are briefly summarized. After that, strategies be summarized, including synthesizing single-component O2DCs dimensional control vdWhs I2DCs. With these approaches, dimension, stacking modes, composition highlighted. Subsequently, special focus given on discussion optical electronic materials closely relevant structures, so that can establish general structure-property relationship In addition properties, devices such transistors, photodetectors, sensors, spintronics, neuromorphic well energy discussed. Finally, provide outlook discuss key challenges future development. This aims foundational understanding inspire further innovation next-generation transformative technological potential.

Language: Английский

Citations

5
Highly Crystalline Helical Covalent Organic Frameworks DOI

Jiang Sun,

Lan Peng,

Yunqi Liu

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(8), P. 3666 - 3672

Published: April 12, 2024

Controllable synthesis of highly crystalline covalent organic frameworks (COFs) with unique structures is important for fundamental research and their practical applications. Herein, we report helical COFs, termed helical-COFTP-Py, synthesized through the Schiff base condensation 1,3,6,8-tetra(4-aminophenyl)-pyrene terephthalaldehyde via supercritically solvothermal polymerization in supercritical carbon dioxide (sc-CO2) as reaction medium. The conditions that affect formation product are investigated. We find interlayer rotation triggered by adsorption CO2, revealing role sc-CO2 crystals. In addition, when 2,5-dihydroxyterephthalaldehyde (DHTP) used monomer, resultant COFDHTP-Py crystals feature a rod-like morphology without structure, indicating hydrogen bonds locking adjacent layers hindering rotation. COF prepared this work high crystallinity, large size, one-dimensional channels, holding promising applications chiral resolution ion separation.

Language: Английский

Citations

2
Band engineering in two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks: insight from molecular design DOI Creative Commons
Xiaojuan Ni, Jean‐Luc Brédas

Deleted Journal, Journal Year: 2024, Volume and Issue: 1(1)

Published: July 4, 2024

Abstract Two-dimensional covalent organic frameworks (2D COFs) represent an emerging class of crystalline polymeric networks, characterized by their tunable architectures and porosity, synthetic adaptability, interesting optical, magnetic, electrical properties. The incorporation porphyrin (Por) or phthalocyanine (Pc) core units into 2D COFs provides ideal platform for exploring the relationship between COF geometric structure its electronic properties in case tetragonal symmetry. In this work, on basis tight-binding models density functional theory calculations, we describe generic types band structures that can arise COFs. Three lattice symmetries are examined: basic square lattice, Lieb checkerboard lattice. potential topological characteristics each explored. Por-/Pc-based exhibit characteristic dispersions directly linked to nature frontier molecular orbitals building units. We show these be tailored choosing specific and/or modulating relative energies linker These strategies extended a wide array COFs, offering effective approach engineering

Language: Английский

Citations

1
Electronic structures of two-dimensional covalent organic frameworks based on a series of period 4 transition metal phthalocyanines and ethynyl moieties DOI
Xin Chen, Xianran Xing

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 5719 - 5724

Published: Jan. 1, 2024

Two-dimensional metal–phthalocyanine-based covalent organic frameworks (MPc COFs) have unique electronic properties to be applied in electrocatalytic and photochemical reactions.

Language: Английский

Citations

1
Computational Design of 3D Lantern Organic Framework DOI Open Access
Lam Nguyen, Thanh N. Truong

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(61)

Published: Aug. 22, 2024

Abstract This study employed a computational approach, particularly Density Functional Theory at B3LYP−D3/6‐31+G(d) level to design two new classes of three‐dimensional (3D) Lantern Organic Frameworks (LOFs) materials based on trisilasumanene and porphyrin core building units. Particularly, we detail strategies for transitioning from 1D‐LOF nanowires extended 3D structures: first by connecting planar‐molecule base units or using benzene‐based linkers, then silicon anchoring atoms the bases with other that are vertically stacked sp 3 ‐hydrocarbon chains. The 3D‐LOF structures designed have different pore sizes through use various bases, bridges, linkers. Comparisons electronic properties these lead one designing rule. That is, gap between highest occupied molecular orbital (HOMO) lowest unoccupied (LUMO) depends only its is nearly independent stack size length bridges. Additionally, linkers also extends π‐electron conjugation system leading reduction in HOMO‐LUMO gap. For instance, linking molecules significantly narrows 1.75 eV while stacking them linear pentane‐based bridges yield insignificant change

Language: Английский

Citations

0