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New Hybrid Materials for Nonlinear Optics
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New Hybrid Materials for Nonlinear Optics

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 6690

Special Issue Editor

Dr. Marek Drozd

E-Mail Website
Guest Editor
Wlodzimierz Trzebiatowski Institute of Low Temperature and Structure Research of the Polish Academy of Sciences, 50-422 Wroclaw, Poland
Interests: spectroscopy of amino-acids and its inorganic-organic complexes; searching for new nonlinear optics (NLO) materials; spectroscopy of monocrystals in polarized light; DFT theoretical calculation; hydrogen bonds

Special Issue Information

Dear colleagues,

From the fundamental science point of view are important common attributes of NLO materials. Firstly, all SHG crystals of these materials should be non-centrosymmetric. The question of how to enforce the crystal structure noncentrosymmetric without engaging intrinsically chiral molecules still seems to be open, but sometimes the creation of weak chemical interaction, such as hydrogen bonds can be deciding about the symmetry of prepared crystals. On the other hand, the influence of hydrogen bonds on the NLO properties of investigated materials is not clear-cut.

In preparation and searching process of new compounds for nonlinear optics, especially compounds capable of the generation of the second harmonic of radiation various tactics are used. Generally, one way is connected with the synthesis of a new inorganic compound, which features relatively low room for improvements of the strength of the NLO effects, but these compounds have very good optical and physical properties such as the growth of large single crystals and durability. On the other hand, the strategy that employs the synthesis of hybrid materials that comprise two parts, organic and inorganic, also gained high popularity.

In the special issue the completely new papers devoted to strategy to merge organic part that may feature high first hyperpolarizability (β) with an inorganic component which can act as a modifier of the nonlinear response, but also can impart better physicochemical properties e.g. durability are welcome.

Dr. Marek Drozd
Guest Editor

Manuscript Submission Information

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Keywords

  • hybrid materials
  • hydrogen bonds
  • weak interaction
  • second harmonic generation
  • nonlinear optics
  • organic-inorganic molecular complexes

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Published Papers (3 papers)

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Research

17 pages, 14811 KiB  
Article
Inorganic Salts of N-phenylbiguanidium(1+)—Novel Family with Promising Representatives for Nonlinear Optics
by Irena Matulková, Ivana Císařová, Michaela Fridrichová, Róbert Gyepes, Petr Němec, Jan Kroupa and Ivan Němec
Int. J. Mol. Sci. 2021, 22(16), 8419; https://doi.org/10.3390/ijms22168419 - 5 Aug 2021
Viewed by 1909
Abstract
Seven inorganic salts containing N-phenylbiguanide as a prospective organic molecular carrier of nonlinear optical properties were prepared and studied within our research of novel hydrogen-bonded materials for nonlinear optics (NLO). All seven salts, namely N-phenylbiguanidium(1+) nitrate (C2/c), [...] Read more.
Seven inorganic salts containing N-phenylbiguanide as a prospective organic molecular carrier of nonlinear optical properties were prepared and studied within our research of novel hydrogen-bonded materials for nonlinear optics (NLO). All seven salts, namely N-phenylbiguanidium(1+) nitrate (C2/c), N-phenylbiguanidium(1+) perchlorate (P-1), N-phenylbiguanidium(1+) hydrogen carbonate (P21/c), bis(N-phenylbiguanidium(1+)) sulfate (C2), bis(N-phenylbiguanidium(1+)) hydrogen phosphate sesquihydrate (P-1), bis(N-phenylbiguanidium(1+)) phosphite (P21), and bis(N-phenylbiguanidium(1+)) phosphite dihydrate (P21/n), were characterised by X-ray diffraction (powder and single-crystal X-ray diffraction) and by vibrational spectroscopy (FTIR and Raman). Two salts with non-centrosymmetric crystal structures—bis(N-phenylbiguanidium(1+)) sulfate and bis(N-phenylbiguanidium(1+)) phosphite—were further studied to examine their linear and nonlinear optical properties using experimental and computational methods. As a highly SHG-efficient and phase-matchable material transparent down to 320 nm and thermally stable to 483 K, bis(N-phenylbiguanidium(1+)) sulfate is a promising novel candidate for NLO. Full article
(This article belongs to the Special Issue New Hybrid Materials for Nonlinear Optics)
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19 pages, 6152 KiB  
Article
DFT Studies of Selected Epoxies with Mesogenic Units–Impact of Molecular Structure on Electro-Optical Response
by Magdalena Włodarska and Beata Mossety-Leszczak
Int. J. Mol. Sci. 2021, 22(7), 3424; https://doi.org/10.3390/ijms22073424 - 26 Mar 2021
Cited by 8 | Viewed by 1854
Abstract
Theoretical studies of molecular structure and electric charge distribution were carried out for three epoxy compounds with different mesogenic cores. The compounds exhibit a nematic phase and form polymer networks that are potential bases for various composites. Results were compared to analogous materials [...] Read more.
Theoretical studies of molecular structure and electric charge distribution were carried out for three epoxy compounds with different mesogenic cores. The compounds exhibit a nematic phase and form polymer networks that are potential bases for various composites. Results were compared to analogous materials with non-polar chains. A customized process involving geometry optimization of a series of conformations was employed to greatly increase likelihood of reaching global energy minimum for each molecule. All computations used Density Functional Theory (DFT) electron correlation model with the B3LYP hybrid functional. Molecular structure calculations yielded several parameters, including the magnitude and direction of the dipole moment, polarizability (α), first hyperpolarizability (β), and highest-occupied/lowest-unoccupied molecular orbital (HOMO-LUMO) energies. These parameters can help predict electronic properties of the nematic phase and the polymer network and assess their predisposition for application in electrooptical devices. In particular, the magnitude and direction of the dipole moment determine molecular alignment of liquid crystal phases in electric field, which enables controlling molecular order also in cured networks. Theoretical results were supplemented with observations of the nematics and their behavior in electric field. It was demonstrated for the studied compounds that a change in aliphatic chain polarity helps preserve and reinforce perpendicular alignment of molecules induced by electric field. Full article
(This article belongs to the Special Issue New Hybrid Materials for Nonlinear Optics)
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22 pages, 5044 KiB  
Article
Studies of Sol-Gel Evolution and Distribution of Eu3+ Ions in Glass–Ceramics Containing LaF3 Nanocrystals Depending on Initial Sols Composition
by Natalia Pawlik, Barbara Szpikowska-Sroka, Tomasz Goryczka and Wojciech A. Pisarski
Int. J. Mol. Sci. 2021, 22(3), 996; https://doi.org/10.3390/ijms22030996 - 20 Jan 2021
Cited by 8 | Viewed by 2314
Abstract
In this work, we performed a systematic analysis of the impact of selected chemical reagents used in sol-gel synthesis (i.e., N,N-dimethylformamide) and different catalyst agents (i.e., CH3COOH, HNO3) on the formation and luminescence of Eu3+-doped SiO2 [...] Read more.
In this work, we performed a systematic analysis of the impact of selected chemical reagents used in sol-gel synthesis (i.e., N,N-dimethylformamide) and different catalyst agents (i.e., CH3COOH, HNO3) on the formation and luminescence of Eu3+-doped SiO2–LaF3 nano-glass–ceramics. Due to the characteristic nature of intra-configurational electronic transitions of Eu3+ ions within the 4f6 manifold (5D0 → 7FJ, J = 0–4), they are frequently used as a spectral probe. Thus, the changes in the photoluminescence profile of Eu3+ ions could identify the general tendency of rare earth materials to segregate inside low-phonon energy fluoride nanocrystals, which allows us to assess their application potential in optoelectronics. Fabricated sol-gel materials, from sols to gels and xerogels to nano-glass–ceramics, were examined using several experimental techniques: X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR), and luminescence measurements. It was found that the distribution of Eu3+ ions between the amorphous silicate sol-gel host and LaF3 nanocrystals is strictly dependent on the initial composition of the obtained sols, and the lack of N,N-dimethylformamide significantly promotes the segregation of Eu3+ ions inside LaF3 nanocrystals. As a result, we detected long-lived luminescence from the 5D0 excited state equal to 6.21 ms, which predisposes the obtained glass–ceramic material for use as an optical element in reddish-orange emitting devices. Full article
(This article belongs to the Special Issue New Hybrid Materials for Nonlinear Optics)
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