Unique anisotropic optical properties of a highly stable metal–organic framework based on trinuclear iron(<scp>iii</scp>) secondary building units linked by tetracarboxylic linkers with an anthracene core

Виноградов, А. В.; Milichko, Valentin A.; Zaake-Hertling, Haldor; Aleksovska, Angela; Gruschinski, Sina; Schmorl, Sara; Kersting, Berthold; Zolnhofer, Eva M.; Sutter, Jörg; Meyer, Karsten; Lönnecke, Peter; Hey‐Hawkins, Evamarie

doi:10.1039/c6dt00390g

Cited by 19 publications

(24 citation statements)

References 42 publications

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“…These materials have proved to be excellent sorbents for gases, objects for storing hydrogen (as fuel), catalysts, elements of analytical devices for separating substances, as well as demonstrating unique physical properties in the field of ferroelectricity, non-linear optics, and magnetism. However, in addition to the existing broad scope of applications mainly due to a huge surface area, recently also unique features such as strong optical anisotropy in the visible region have been studied, 32 which were detected via reflection/ absorption spectra ( Fig. 8), depending on the direction of the polarization vector.…”

Section: Metal-organic Frameworkmentioning

confidence: 99%

“…in the channels allows to perform all optical experiments with the single crystal consecutively or two experiments simultaneously (e.g., luminescence and transmission). This system is well described 32 and allows studying non-linear optical effects (exciton luminescence or birefringence) in different points of single microcrystals.…”

Section: The Relationship Between the Shg And The Size Of The Crystalmentioning

confidence: 99%

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Metal–organic frameworks as competitive materials for non-linear optics

et al. 2016

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The last five years have witnessed a huge breakthrough in the creation and the study of the properties of a new class of compounds - metamaterials. The next stage of this technological revolution will be the development of active, controllable, and non-linear metamaterials, surpassing natural media as platforms for optical data processing and quantum information applications. However, scientists are constantly faced with the need to find new methods that can ensure the formation of quantum and non-linear metamaterials with higher resolution. One such method of producing metamaterials in the future, which will provide scalability and availability, is chemical synthesis. Meanwhile, the chemical synthesis of organized 3D structures with a period of a few nanometers and a size of up to a few millimeters is not an easy task and is yet to be resolved. The most promising avenue seems to be the use of highly porous structures based on metal-organic frameworks that have demonstrated their unique properties in the field of non-linear optics (NLO) over the past three years. Thus, the aim of this review is to examine current progress and the possibilities of using metal-organic frameworks in the field of non-linear optics as chemically obtained metamaterials of the future. The review begins by presenting the theoretical principles of physical phenomena represented by mathematical descriptions for clarity. Major attention is paid to the second harmonic generation (SHG) effect. In this section we compare inorganic single crystals, which are most commonly used to study the effect in question, to organic materials, which also possess the required properties. Based on these data, we present a rationale for the possibility of studying the non-linear optical properties of metal-organic structures as well as describing the use of synthetic approaches and the difficulties associated with them. The second part of the review explicitly acquaints the reader with a new class of materials which successfully combines the positive properties of organic and inorganic materials. Using recently synthesized metal-organic frameworks and coordination polymers in the field of non-linear optics as an example, we consider synthetic approaches used for obtaining materials with desired properties and the factors to be considered in this case. Finally, probable trends towards improving the quality of the synthesized materials with regards to their further use in the field of non-linear optical effects are described.

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Section: Metal-organic Frameworkmentioning

confidence: 99%

Section: The Relationship Between the Shg And The Size Of The Crystalmentioning

confidence: 99%

Metal–organic frameworks as competitive materials for non-linear optics

et al. 2016

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“…For excitons, the quantum states of electrons and holes are correlated, and they are thus considered as a single particle that has a hydrogen-like energy spectrum lying within the bandgap. [43] Exciton complexes, such as biexcitons, and indirect excitons, can also be manipulated by optical, electric, and magnetic fields and tuneable structures. For molecular crystals and low-dimensional structures, the binding energy of an exciton can be much higher than the thermal energy (0.026 eV).…”

Section: Excitonsmentioning

confidence: 99%

“…Such a high binding energy (>0.1 eV), allowing the exciton to exist at room temperature, is a key aspect for applications such as excitonic lasers, valeytronics, and organic solar cells . Moreover, the exciton is such a specific particle that its migration within a structure ( Figure a) can be driven by external stimuli or structural anisotropy . Exciton complexes, such as biexcitons, and indirect excitons, can also be manipulated by optical, electric, and magnetic fields and tuneable structures.…”

Section: Transfer Effects In Mofsmentioning

confidence: 99%

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives

et al. 2019

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Owing to the synergistic combination of a hybrid organic–inorganic nature and a chemically active porous structure, metal–organic frameworks have emerged as a new class of crystalline materials. The current trend in the chemical industry is to utilize such crystals as flexible hosting elements for applications as diverse as gas and energy storage, filtration, catalysis, and sensing. From the physical point of view, metal–organic frameworks are considered molecular crystals with hierarchical structures providing the structure‐related physical properties crucial for future applications of energy transfer, data processing and storage, high‐energy physics, and light manipulation. Here, the perspectives of metal–organic frameworks as a new family of functional materials in modern physics are discussed: from porous metals and superconductors, topological insulators, and classical and quantum memory elements, to optical superstructures, materials for particle physics, and even molecular scale mechanical metamaterials. Based on complementary properties of crystallinity, softness, organic–inorganic nature, and complex hierarchy, a description of how such artificial materials have extended their impact on applied physics to become the mainstream in material science is offered.

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“…17,28 The lack of precise optical characterization may be due to the notorious difficulty of growing large singlecrystals MOFs. 31,32 From the vast MOF literature, only a few reports of single-crystals MOFs grown beyond one millimeter can be found. [33][34][35][36] Although efforts to understand the dynamics of self-assembly process in MOFs under solvothermal conditions are underway, 37,38 a general understanding of this process is still elusive, limiting the available strategies for the growth of single-crystals for optical devices.…”

Section: Introductionmentioning

confidence: 99%

Anisotropic Band-Edge Absorption of Millimeter-Size Zn(3-Ptz)2 Single Crystal Metal-Organic Frameworks

Chi-Durán¹,

Fritz²,

Olaya³

et al. 2020

Preprint

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<div><div><div><p>Metal-organic frameworks (MOF) have emerged as promising tailor-design materials for developing next-generation solid-state devices with applications in linear and non-linear coherent optics. However, the implementation of functional devices is challenged by the notoriously difficult process of growing large MOF single-crystals of high optical quality. By controlling the solvo-thermal synthesis conditions, we succeed in producing large individual single crystals of the non-centrosymmetric MOF Zn(3-ptz)2 (MIRO-101) with deformed octahedron habit, and unprecedented surface areas of up to 37 mm<sup>2</sup>. We measure the polarized UV-visible absorption spectrum of individual Zn(3- ptz)2 single crystals across different lateral incidence planes. Millimeter size single crystals have band gap <i>E</i><i>g</i> = 3.32 eV, and exhibit anisotropic absorption in the band edge region near 350 nm, whereas polycrystalline samples are fully transparent in the same frequency range. Using solid-state density functional theory (DFT), the observed size dependence of the optical anisotropy is correlated with the preferred orientation adopted by freely rotating pyridyl groups under conditions of slow crystal self-assembly. Our work thus paves the way for the development of optical polarization switches based on metal-organic frameworks.</p></div></div></div>

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Unique anisotropic optical properties of a highly stable metal–organic framework based on trinuclear iron(iii) secondary building units linked by tetracarboxylic linkers with an anthracene core

Cited by 19 publications

References 42 publications

Metal–organic frameworks as competitive materials for non-linear optics

Metal–organic frameworks as competitive materials for non-linear optics

Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives

Anisotropic Band-Edge Absorption of Millimeter-Size Zn(3-Ptz)2 Single Crystal Metal-Organic Frameworks

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