Morphology-dependent third-order optical nonlinearity of a 2D Co-based metal–organic framework with a porphyrinic skeleton

Niu, Ru-Jie; Zhou, Wenfa; Liu, Yan; Yang, Junyi; Zhang, Wen Hua; Lang, Jian‐Ping; Young, David J.

doi:10.1039/c9cc01363f

Cited by 40 publications

(19 citation statements)

References 82 publications

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“…28,29 As a branch of MOFs, porphyrinic MOFs 30 are attracting great attention on the third-order NLO performance because of their highly delocalized π-electronic conjugated system. 31,32 Generally, 3D porous porphyrinic MOFs with a weak π−π interaction have greatly limited performance, and they usually need to be loaded with guest species in their pores to enhance the third-order NLO performance. 33,34 Instead, 2D porphyrinic MOFs possess a huge number of π−π interactions between layers.…”

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confidence: 99%

Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework Films for Giant Nonlinear Optical Limiting

et al. 2021

Nano Lett.

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The development of metal–organic frameworks (MOFs) with nonlinear optical (NLO) properties is of pronounced significance for optical devices. Herein, a series of 2D MOFs ZnTPyP(M) (TPyP = 5,10,15,20-tetrakis(4-pyridyl)porphyrin, M = Cu, Ni, Mn, H2) films with [010]-orientation growth composed of ultrathin nanosheets from a pyridylporphyrinic ligand are first obtained by using a liquid-phase epitaxial (LPE) layer-by-layer (lbl) growth approach. ZnTPyP(M) films show a giant nonlinear optical limiting (OL) response and can be modulated by tuning the type of metalloporphyrinic ligands. As a result, ZnTPyP(Cu) film exhibits the highest nonlinear absorption coefficient of 5.7 × 10–6 m/W compared to other reported NLO materials. Density functional theory calculations were consistent with the experimental results, revealing that the tunable π–π* local excitation and the increased delocalization of the metalloporphyrinic group regulate the NLO performance of ZnTPyP(M) films. These findings provide new insight into the effect of 2D porphyrinic MOFs toward the NLO response and offer new film candidates for nonlinear OL application.

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confidence: 99%

Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework Films for Giant Nonlinear Optical Limiting

et al. 2021

Nano Lett.

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“…Other experimental conditions for these NLO measurements were the same as described in our previous articles. [ 18,20,51 ]…”

Section: Methodsmentioning

confidence: 99%

Butterfly and Nest‐Shaped Tp*‐W‐Cu‐S Cluster Monomers and Dimers with Hexamethylenetetramine as Ligand: Anion‐Dependent Structures and Nonlinear Optical Properties

Liu

et al. 2021

Chin. J. Chem.

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Main observation and conclusion The assembly of [Et4N][Tp*WS3] (1) with CuX (Tp* = hydridotris(3,5‐dimethylpyrazol‐1‐yl)borate; X = Cl, Br, and I) or [Cu(MeCN)4][PF6] in the presence of tetratopic ligand hexamethylenetetramine (HMT) afforded an array of four cluster‐based compounds, which are either neutral or anionic. These compounds include [Tp*WS3Cu3Cl2(HMT)] (2, monomer, neutral), [Tp*WS3Cu3Br2(HMT)] (3, monomer, neutral), [Tp*WS3Cu3I1.5(HMT)]2I (4, dimer, anionic), and [Tp*WS3Cu2(HMT)]2(PF6)2 (5, dimer, anionic). The size of the halogen is found to dictate the structures (2/3 versus 4), and the presence/absence of halogen also affects the utilization of coordinate site of HMT (4 versus 5) by creating more available Cu(I) site in the case of 5. The structures of 2—5 are also characterized using elemental analysis, Fourier‐transform infrared (FT‐IR) spectra, and ultraviolet‐visible (UV‐Vis) spectroscopy, with the dimeric structure of 5 also selected for the third‐order nonlinear optical (NLO) property investigations. The NLO measurement results suggest that the hyperpolarizability value (γ) of 5, reflecting its NLO properties as a neat material, features 2.12×10−30 esu, and it is comparable to other W/Cu/S cluster‐based molecular entities, rendering 5 a promising NLO‐active material.

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“…1) for efficient catalysis [27]. Thermally stable metalloporphyrins [28][29][30] are used as a building block, while diacetylene moieties function for the topochemical thermal polymerization to construct rigid three dimensional frameworks, enabling the structure retention upon the pyrolysis. More recently, we have synthesized OCFs also from Ni porphyrin with ethynyl groups as a thermally polymerizable moiety [31].…”

Section: Introductionmentioning

confidence: 99%

Iron porphyrin-derived ordered carbonaceous frameworks

et al. 2021

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Morphology-dependent third-order optical nonlinearity of a 2D Co-based metal–organic framework with a porphyrinic skeleton

Abstract: A two-dimensional (2D) Co-based metal–organic framework (MOF) with a porphyrinic skeleton forms crystalline plates, flower-shaped clusters, and ultrathin films under optimized conditions and these forms give distinctively different nonlinear optical properties.

Cited by 40 publications

References 82 publications

Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework Films for Giant Nonlinear Optical Limiting

Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework Films for Giant Nonlinear Optical Limiting

Butterfly and Nest‐Shaped Tp*‐W‐Cu‐S Cluster Monomers and Dimers with Hexamethylenetetramine as Ligand: Anion‐Dependent Structures and Nonlinear Optical Properties

Iron porphyrin-derived ordered carbonaceous frameworks

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