Giant and Multistage Nonlinear Optical Response in Porphyrin-Based Surface-Supported Metal–Organic Framework Nanofilms

Gu, Chun; Zhang, Hang; You, Pengxian; Zhang, Qiao; Luo, Guoqiang; Shen, Qiang; Wang, Zhengbang; Hu, Jianbo

doi:10.1021/acs.nanolett.9b04221

Cited by 84 publications

(68 citation statements)

References 53 publications

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“…[201] More recently,d onor-acceptor interactions between electron-acceptor porphyrin-based 2D MOF and electron-acceptorC 60 were demonstrated to enhancet he photoconductivity. [202] Light-harvesting [204] and non-linear optical (NLO) properties [205] of some porphyrin-based MOFs have also been studied taking advantage of their optical properties. The first example of ap hthalocyanine-based MOF was reported in 2018 based on tetracatechol copper Pcs ligands bridged by square-planarC u II ions.…”

Section: Porphyrin (Por)mentioning

confidence: 99%

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Souto

Strutyński

Melle‐Franco

et al. 2020

Chemistry A European J

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Electroactive organic molecules have received a lot of attention in the field of electronics because of their fascinating electronic properties, easy functionalization and potential low cost towards their implementation in electronic devices. In recent years, electroactive organic molecules have also emerged as promising building blocks for the design and construction of crystalline porous frameworks such as metal–organic frameworks (MOFs) and covalent‐organic frameworks (COFs) for applications in electronics. Such porous materials present certain additional advantages such as, for example, an immense structural and functional versatility, combination of porosity with multiple electronic properties and the possibility of tuning their physical properties by post‐synthetic modifications. In this Review, we summarize the main electroactive organic building blocks used in the past few years for the design and construction of functional porous materials (MOFs and COFs) for electronics with special emphasis on their electronic structure and function relationships. The different building blocks have been classified based on the electronic nature and main function of the resulting porous frameworks. The design and synthesis of novel electroactive organic molecules is encouraged towards the construction of functional porous frameworks exhibiting new functions and applications in electronics.

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Section: Porphyrin (Por)mentioning

confidence: 99%

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Souto

Strutyński

Melle‐Franco

et al. 2020

Chemistry A European J

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“…[71] This should result in much larger nonlinearities compared to MOFs with centrosymmetric structures, which exploit second-order nonlinear effects. [72] In fact, the realization of polar MOFs could boost the applicability of MOFs in nonlinear optics and might well help overcoming the challenge of properly aligning first-order NLO chromophores. [71] This would enable the use of MOFs in applications like second harmonic generation, or electrooptic switching.…”

Section: Discussionmentioning

confidence: 99%

Electrostatic Design of Polar Metal–Organic Framework Thin Films

2020

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In recent years, optical and electronic properties of metal–organic frameworks (MOFs) have increasingly shifted into the focus of interest of the scientific community. Here, we discuss a strategy for conveniently tuning these properties through electrostatic design. More specifically, based on quantum-mechanical simulations, we suggest an approach for creating a gradient of the electrostatic potential within a MOF thin film, exploiting collective electrostatic effects. With a suitable orientation of polar apical linkers, the resulting non-centrosymmetric packing results in an energy staircase of the frontier electronic states reminiscent of the situation in a pin-photodiode. The observed one dimensional gradient of the electrostatic potential causes a closure of the global energy gap and also shifts core-level energies by an amount equaling the size of the original band gap. The realization of such assemblies could be based on so-called pillared layer MOFs fabricated in an oriented fashion on a solid substrate employing layer by layer growth techniques. In this context, the simulations provide guidelines regarding the design of the polar apical linker molecules that would allow the realization of MOF thin films with the (vast majority of the) molecular dipole moments pointing in the same direction.

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“…[166][167][168] Gu et al prepared crystalline and highly oriented surfacesupported MOF nanofilms (SURMOFs) by the layer-by-layer liquid-phase epitaxial technique. [169] The 3D porphyrin-based SURMOFs are constructed by linking Co-oxo trinuclear clusters and porphyrin molecules ( [5,10,15,20-(4-carboxyphenyl) porphyrin], TCPP) (Figure 5a). Due to the strong π-electron delocalization effect in porphyrin arrays, porphyrin-based SURMOFs exhibit marked NLO properties.…”

Section: Organic/inorganic Hybrid Porous Materials For Third-order Nlomentioning

confidence: 99%

“…Reproduced with permission. [169] Copyright 2019, American Chemical Society. d) The preparation of PIZA-1 and C 60 @PIZA-thin film by autoarm immersion layer-by-layer method and tunable NLO behavior by tuning the thickness and loading fullerene molecules.…”

Section: Organic/inorganic Hybrid Porous Materials For Third-order Nlomentioning

confidence: 99%

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Crystalline Porous Materials for Nonlinear Optics

Shi

Han

et al. 2021

Small

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metal chalcogenides, [17,18] graphdiyne, [19][20][21] etc.) and perovskites [22][23][24][25][26] have been in a state of vigorous development and rapid advances for applications in optoelectronics, catalysis, energy conversion, due to their autologous admirable chemistry and physics characteristics. [27,28] Porous materials, a scientifically evolving and functionally compelling class of solid compounds with well-defined pore structures, such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and polyoxometalates (POMs), have attracted broad research interest because of their wide applications in many fields including, but not limited to, adsorption, separation, catalysis, and photovoltaics. [29][30][31][32] Through fine control over the organic units to create predesigned skeletons, an exceptionally large set of materials with unique porous structures and remarkable properties have been developed. [33,34] MOFs, also known as coordination polymers or coordination networks, are one class of crystalline porous materials prepared by the self-assembly of metal ions or clusters with organic ligands. [35] They have drawn tremendous research interest for their customizable chemical structures along with unique chemical and physical properties, [36][37][38][39][40][41] which guarantee their wide applications as adsorption and separation, catalysts, magnetic, and light emitting materials. [36,[42][43][44][45] The use of appropriate ligands with optimized electronic push-pull structures, the degree of conjugation in the system and the encapsulation of guest molecules with different properties are some of the effective strategies to enhance the linear and nonlinear optical properties of the MOFs materials. [46][47][48] COFs, constructed from organic moltifs linking through strong covalent bonding, are a kind of crystalline porous materials in which the atoms of organic units are precisely integrated to create periodic frameworks and nanopores. [49,50] Although the thermal stability and crystallinity of COFs are lower than MOFs, they have received wide attention due to their low density, large surface area and strong ππ stacking. [51][52][53][54] It has been appreciated that the applications of COFs materials in third-order NLO such as two-photon fluorescence have been well developed in recent years. [55][56][57] Similar to MOFs and COFs, POMs formed by the coordination of early transition metals and oxygen atoms are a class of crystalline porous materials with unique structures and properties for their exceptional crystallinity and high stability. [58] POMs are intrinsically electron deficient, and their electronaccepting capability in combination with highly delocalized π-conjugated systems is particularly promising for producing NLO materials. [59,60] The structure of all the crystalline porous Crystalline porous materials have been extensively explored for wide applications in many fields including nonlinear optics (NLO) for frequency doubling, two-photon absorption/emission, optical limiting effect,...

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Giant and Multistage Nonlinear Optical Response in Porphyrin-Based Surface-Supported Metal–Organic Framework Nanofilms

Cited by 84 publications

References 53 publications

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Electroactive Organic Building Blocks for the Chemical Design of Functional Porous Frameworks (MOFs and COFs) in Electronics

Electrostatic Design of Polar Metal–Organic Framework Thin Films

Crystalline Porous Materials for Nonlinear Optics

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