Developing new SrI2 and β-D-fructopyranose-based metal–organic frameworks with nonlinear optical properties

In the context of personalized medicine, there is a growing interest in materials bearing at the same time diagnostic and therapy functions. This article reports a cheap and easily reproducible procedure to obtain materials with a high potential for these applications. Three new strontium iodide–fructose-based metal–organic frameworks with formulae [Sr(C6H12O6)2]I2, [Sr2(C6H12O6)3(H2O)3]I4·0.5H2O and [Sr(C6H12O6)(H2O)3I]I differing in stoichiometry, symmetry and crystal packing, were obtained and characterized by X-ray diffraction. Bulk quantum simulations show that both the ions and the sugar are crucial in determining the predicted nonlinear response; also, the relative arrangement of various functional groups in the unit cell plays a role in the computed optical properties. Small fragments of the three compounds were selected for in vacuo calculations, proving that the reduced dimensions of the particles have a great influence on the nonlinear optical response. Despite the similar chemical composition of the three compounds, second harmonic generation measurements and in crystal and in vacuo theoretical calculations agree that one of the compounds is a much more efficient second harmonic emitter than the other two, and is thus a suitable candidate for bio-sensor applications.

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Crystal structure or chemical composition of salt–sugar-based metal–organic frameworks: what are the nonlinear optical properties due to?

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520621004637 ◽

2021 ◽

Vol 77 (4) ◽

Author(s):

Domenica Marabello ◽

Paola Antoniotti ◽

Paola Benzi ◽

Fabio Beccari ◽

Carlo Canepa ◽

...

Keyword(s):

Optical Properties ◽

Crystal Engineering ◽

Density Functional ◽

Nonlinear Optical ◽

Second Harmonic ◽

Imaging Techniques ◽

Metal Organic Frameworks ◽

Nonlinear Optical Properties ◽

Crystal Density ◽

Metal Organic

In the last few decades optical imaging techniques based on nonlinear optical properties have been of interest for biosensing applications. This work focuses on two isostructural and isomorphous sugar-derived metal–organic frameworks (MOFs) with second-harmonic generation (SHG) properties, in order to investigate their possible application as biosensors in view of their high biocompatibility. Combining 2-deoxy-D-galactose with the metal halogenides CaX 2 (X = Br, I), two new isomorphous MOFs of formula [Ca(C6H12O5)2]X 2 were obtained and characterized through single-crystal X-ray diffraction. The first-order static hyperpolarizability and second-order susceptibility were estimated by in vacuo and in-crystal density functional theory calculations, and compared with the experimental SHG response of powdered samples. The parameters influencing the SHG response of these compounds were investigated by comparison with similar previously analysed MOFs, to understand how to design more efficient materials to be used as nanoprobes by exploiting crystal engineering techniques.

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Encapsulation of dyes in metal–organic frameworks and their tunable nonlinear optical properties

Dalton Transactions ◽

10.1039/c5dt03466c ◽

2016 ◽

Vol 45 (10) ◽

pp. 4218-4223 ◽

Cited By ~ 30

Author(s):

Tao Song ◽

Jiancan Yu ◽

Yuanjing Cui ◽

Yu Yang ◽

Guodong Qian

Keyword(s):

Optical Properties ◽

Nonlinear Optical ◽

Metal Organic Frameworks ◽

Second Order ◽

Nonlinear Optical Properties ◽

Cationic Dyes ◽

Metal Organic

Two series of cationic dyes have been encapsulated in the 1D channel of MOFs, and the tunable second order nonlinear optical properties of these MOF⊃dye materials were observed.

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The nonlinear optical susceptibility and electro-optic tensor of ferroelectrics: first-principle study

Open Physics ◽

10.2478/s11534-011-0079-3 ◽

2012 ◽

Vol 10 (1) ◽

Cited By ~ 9

Author(s):

Suleyman Cabuk

Keyword(s):

Optical Properties ◽

Band Gap ◽

Density Functional ◽

Nonlinear Optical ◽

Local Density ◽

Second Harmonic ◽

Theoretical Calculations ◽

Nonlinear Optical Properties ◽

First Principle ◽

Electro Optic

AbstractThe nonlinear optical properties of some ABO3 materials (BaTiO3, KNbO3, LiTaO3 and LiNbO3) are studied by density functional theory (DFT) in the local density approximation (LDA) expressions based on first-principle calculations. Our goals are to give the details of the calculations for linear and nonlinear optical properties, including the linear electro-optic (EO) tensor for some ABO3 structures with oxygen octahedral structures using first-principles methods. These results can then be used in the study of the physics of ferroelectrics, specifically, we present calculations of the second harmonic generation response coefficient X ijk(2) (−2ω, ω, ω) over a large frequency range for ABO3 crystals. The electronic linear EO susceptibility X ijk(2) (−ω, ω,0) is also evaluated below the band gap. These results are based on a series of the LDA calculations using DFT. Results for X ijk(2) (−ω, ω,0) are in agreement with experiments below the band gap. The results are compared with the theoretical calculations and the available experimental data.

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Synthesis, structure and non-linear optical properties of new isostructural β-D-fructopyranose alkaline halide metal–organic frameworks: a theoretical and an experimental study

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520617005285 ◽

2017 ◽

Vol 73 (4) ◽

pp. 737-743 ◽

Cited By ~ 3

Author(s):

Domenica Marabello ◽

Paola Antoniotti ◽

Paola Benzi ◽

Carlo Canepa ◽

Leonardo Mortati ◽

...

Keyword(s):

Optical Properties ◽

Second Harmonic ◽

Theoretical Calculations ◽

Metal Organic Framework ◽

X Ray Diffraction ◽

Intrinsic Nature ◽

Non Linear ◽

Metal Organic ◽

Linear Optical Properties ◽

Linear Optical

In this work four metal–organic framework isomorphs, based on fructose and alkali-earth halogenides, were investigated to better understand the effect of the size of the cation and the different polarizability of the anion on the calculated hyperpolarizability and optical susceptibility, which are correlated to non-linear optical properties. The compounds were characterized by X-ray diffraction and the first hyperpolarizability and the second-order susceptibility were obtained from theoretical calculations. Furthermore, a new method to measure the second-harmonic (SH) efficiency on a small quantity of powder at different wavelengths of excitation was optimized and an attempt was made to assess the reduction of the SH intensity for small quantities of nano-crystals, in order to ascertain the possibility of applications in biological systems. The results of this work show that both the intrinsic nature of the anion and the induced dissociation of cations and anions by fructose play a role in the second-harmonic generating properties of such compounds.

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Nonlinear optical properties, upconversion and lasing in metal–organic frameworks

Chemical Society Reviews ◽

10.1039/c7cs00162b ◽

2017 ◽

Vol 46 (16) ◽

pp. 4976-5004 ◽

Cited By ~ 227

Author(s):

Raghavender Medishetty ◽

Jan K. Zaręba ◽

David Mayer ◽

Marek Samoć ◽

Roland A. Fischer

Keyword(s):

Optical Properties ◽

Coordination Polymers ◽

Building Block ◽

Nonlinear Optical ◽

Metal Organic Frameworks ◽

Nonlinear Optical Properties ◽

Modular Approach ◽

Vast Array ◽

Metal Organic

The building block modular approach that lies behind coordination polymers (CPs) and metal–organic frameworks (MOFs) results not only in a plethora of materials that can be obtained but also in a vast array of nonlinear optical properties that could be aimed at.

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Understanding the Linear and Second-Order Nonlinear Optical Properties of UiO-66-Derived Metal–Organic Frameworks: A Comprehensive DFT Study

The Journal of Physical Chemistry C ◽

10.1021/acs.jpcc.0c01580 ◽

2020 ◽

Vol 124 (21) ◽

pp. 11595-11608

Author(s):

Bilian Ni ◽

Weiming Sun ◽

Jie Kang ◽

Yongfan Zhang

Keyword(s):

Optical Properties ◽

Nonlinear Optical ◽

Metal Organic Frameworks ◽

Second Order ◽

Nonlinear Optical Properties ◽

Dft Study ◽

Metal Organic

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Synthesis and Characterization of New Lithium and Boron Based Metal Organic Frameworks with NLO Properties for Application in Neutron Capture Therapy

Processes ◽

10.3390/pr8050558 ◽

2020 ◽

Vol 8 (5) ◽

pp. 558

Author(s):

Domenica Marabello ◽

Paola Benzi ◽

Fabio Beccari ◽

Carlo Canepa ◽

Elena Cariati ◽

...

Keyword(s):

Neutron Capture ◽

Second Harmonic ◽

Theoretical Calculations ◽

Metal Organic Frameworks ◽

Neutron Capture Therapy ◽

Nlo Property ◽

Thermal Neutron Irradiation ◽

Metal Organic ◽

Natural Isotopes ◽

Physics Department

In this work, we synthetized and characterized new crystalline materials with theranostic properties, i.e., they can be used both as bio-sensors and for “drug delivery”. The two solid crystalline compounds studied are Metal Organic Frameworks and have formulas Li[(C6H12O6)2B]·2H2O and Li[(C4H2O6)2B]·5.5H2O. They can be synthetized both with natural isotopes of Li and B or with 6Li and 10B isotopes, that can be explored for Neutron Capture Therapy (NCT) for anti-cancer treatment. The presence of chiral organic molecules, such as mannitol and tartaric acid, provides the NLO property to the crystals and thus their capability to generate the Second Harmonic, which is useful for applications as bio-sensors. The two compounds were characterized with X-ray Diffraction and the Second Harmonic Generation (SHG) responses were estimated by theoretical calculations, and the results were compared with experimental measurements of powdered samples. In order to test the behavior of such compounds under thermal neutron irradiation, we preliminary exposed one of the two compounds in the e_LiBANS facility at the Torino Physics Department. Preliminary results are reported.

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Controlled Growth of the Non-centrosymmetric Zn(3-ptz)2 and Zn(Oh)(3-ptz) Metal-organic Frameworks

10.26434/chemrxiv.7588640.v1 ◽

2019 ◽

Author(s):

javier enriquez ◽

Ignacio Chi-Duran ◽

Carolina Manquian ◽

Felipe Herrera ◽

Ruben Fritz ◽

...

Keyword(s):

Single Crystal ◽

Nonlinear Optical ◽

Metal Organic Frameworks ◽

Molar Ratio ◽

Thermal Synthesis ◽

Small Crystals ◽

Alkaline Environments ◽

Potential Applications ◽

Metal Organic ◽

Long Rod

Non-centrosymmetric single-crystal metal-organic frameworks (MOF) are promising candidates for phase-matched nonlinear optical communication, but typical hydrothermal synthesis produces small crystals with relatively low transmittance and poor phase matching. We study the effect of the metal-to-ligand molar ratio and reaction pH on the hydro-thermal synthesis of the non-centrosymmetric Zn(3-ptz)2 and Zn(OH)(3-ptz) MOFs with in-situ ligand formation. In acidic environments, we find that decreasing the amount of ligand below the stoichiometric molar ratio 1:2 also produces highly transparent single-crystal octahedrons of Zn(3-ptz)2. In alkaline environments, we obtain long rod-like Zn(OH)(3-ptz) crystals whose length exceeds previous reports by up to four orders of magnitude. Potential applications of these results in the development of MOF-based nonlinear optical devices are discussed.

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