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Metal Complexes for Optical and Electronics Applications
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Metal Complexes for Optical and Electronics Applications

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Applied Chemistry".

Deadline for manuscript submissions: 30 April 2024 | Viewed by 9161

Special Issue Editors

Prof. Dr. Paola Deplano

E-Mail Website
Guest Editor
External Collaborator at Università degli Studi di Cagliari, Cagliari, CA, Italy
Interests: transition metal-complexes; linear and non-linear optics; non-innocent sulphur ligands; donor-acceptor adducts; noble-metals recovery
Special Issues, Collections and Topics in MDPI journals
Dr. Flavia Artizzu

E-Mail Website
Guest Editor
Department of Sciences and Technological Innovation, University of Eastern Piedmont “Amedeo Avogadro”, Viale Teresa Michel 11, 15112 Alessandria, Italy
Interests: lanthanides; luminescence; spectroscopy; coordination chemistry; hybrid materials; photophysics
Special Issues, Collections and Topics in MDPI journals
Dr. Luca Pilia

E-Mail Website
Guest Editor
Dipartimento di Ingegneria Meccanica, Chimica e dei Materiali, Università di Cagliari, Via Marengo 2, 09123 Cagliari, Italy
Interests: coordination chemistry; transition metal-complexes; molecular materials; linear and non-linear optics; non-innocent sulphur ligands; DFT calculations

Special Issue Information

Dear Colleagues,

Metal complexes represent a very large class of molecules which show a variety of chemical and physical properties with important consequences at biological and technological levels. Among the properties presented by metal complexes, catalytic, redox, magnetic, conducting, and optical functionalities are worthy of attention. Moreover, the possibility to change the characteristics of the metal (element and/or oxidation state), along with a proper design of the ligands, allows fine tuning these chemical and physical properties. Currently, metal complexes are attracting great interest in materials science due to their diverse optoelectronic and magnetic properties. The design of such compounds comprises mononuclear as well as polynuclear discrete molecules, supramolecular assemblies, and coordination polymers of various dimensionality, where the resulting morphology often determines an added property.

This Special Issue is devoted to collecting valued contributions on metal complexes, including lanthanide ones, interacting with photons and electrons to achieve absorption, emission, nonlinear optical, photo-switchable, and conducting properties, as well as valued related aspects for optical and electronic applications, including newly emerging quantum technologies. All scientists working in these fields are invited to submit their works for publication in this Special Issue.

Prof. Dr. Paola Deplano
Dr. Flavia Artizzu
Dr. Luca Pilia
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • coordination chemistry
  • metal complexes
  • transition metals
  • lanthanides
  • luminescence
  • nonlinear optics
  • photo-switching
  • conductivity

Published Papers (7 papers)

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Research

18 pages, 3614 KiB  
Article
Dual-Emissive Rectangular Supramolecular Pt(II)-p-Biphenyl with 4,4′-Bipyridine Derivative Metallacycles: Stepwise Synthesis and Photophysical Properties
by Antonia Garypidou, Konstantinos Ypsilantis, John C. Plakatouras and Achilleas Garoufis
Molecules 2023, 28(21), 7261; https://doi.org/10.3390/molecules28217261 - 25 Oct 2023
Viewed by 821
Abstract
Mixed-ligand tetranuclear supramolecular coordination complexes (SCCs) of Pt(II)-p-biphenyl and bridging ligands derivatives of 4,4′-bypiridine (8)–(10), were synthesized and characterized. The SCCs were synthesized stepwise, starting from the Pt-p-biphenyl -Pt core. The crystal structure of complex [...] Read more.
Mixed-ligand tetranuclear supramolecular coordination complexes (SCCs) of Pt(II)-p-biphenyl and bridging ligands derivatives of 4,4′-bypiridine (8)–(10), were synthesized and characterized. The SCCs were synthesized stepwise, starting from the Pt-p-biphenyl -Pt core. The crystal structure of complex {[Pt(2,2′-bpy)]4(μ-bph)2(μ-(4,4′-bpy)2}{PF6}4 (2,2′-bpy = 2,2′-bipyridine, bph = p-biphenyl and 4,4′-bpy = 4,4′ bipyridine), was determined using single-crystal diffraction methods. The emission profile of the tetranuclear complexes (8)–(10) was influenced by the length of the bridging ligands and was found to depend on solvent polarity. Dual-emission patterns in methanol–water mixtures were observed only in the cases of complexes (9) and (10), attributed to aggregation-induced emission phenomena. Full article
(This article belongs to the Special Issue Metal Complexes for Optical and Electronics Applications)
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12 pages, 6386 KiB  
Article
Structural Evolution and Properties of Praseodymium Antimony Oxochlorides Based on a Chain-like Tertiary Building Unit
by Wei-Yang Wen, Bing Hu, Tian-Yu Pan, Zi-Wei Li, Qian-Qian Hu and Xiao-Ying Huang
Molecules 2023, 28(6), 2725; https://doi.org/10.3390/molecules28062725 - 17 Mar 2023
Cited by 2 | Viewed by 1038
Abstract
Unveiling the structural evolution of single-crystalline compounds based on certain building units may help greatly in guiding the design of complex structures. Herein, a series of praseodymium antimony oxohalide crystals have been isolated under solvothermal conditions via adjusting the solvents used, that is, [...] Read more.
Unveiling the structural evolution of single-crystalline compounds based on certain building units may help greatly in guiding the design of complex structures. Herein, a series of praseodymium antimony oxohalide crystals have been isolated under solvothermal conditions via adjusting the solvents used, that is, [HN(CH2CH3)3][FeII(2,2′-bpy)3][Pr4Sb12O18Cl15]·EtOH (1) (2,2′-bpy = 2,2′-bipyridine), [HN(CH2CH3)3][FeII(2,2′-bpy)3]2[Pr4Sb12O18Cl14)2Cl]·N(CH2CH3)3·2H2O (2), and (H3O)[Pr4Sb12O18Cl12.5(TEOA)0.5]·2.5EtOH (3) (TEOA = mono-deprotonated triethanolamine anion). Single-crystal X-ray diffraction analysis revealed that all the three structures feature an anionic zig-zag chain of [Pr4Sb12O18Cl15−x]n as the tertiary building unit (TBU), which is formed by interconnections of praseodymium antimony oxochloride clusters (denoted as {Pr4Sb12}) as secondary building units. Interestingly, different arrangements or linkages of chain-like TBUs result in one-dimensional, two-dimensional layered, and three-dimensional structures of 1, 2, and 3, respectively, thus demonstrating clearly the structural evolution of metal oxohalide crystals. The title compounds have been characterized by elemental analysis, powder X-ray diffraction, thermogravimetric analysis, and UV-Vis spectroscopy, and the photodegradation for methyl blue in an aqueous solution of compound 1 has been preliminarily studied. This work offers a way to deeply understand the assembly process of intricate lanthanide-antimony(III) oxohalide structures at the atomic level. Full article
(This article belongs to the Special Issue Metal Complexes for Optical and Electronics Applications)
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12 pages, 3361 KiB  
Article
Near-IR Absorbers Based on Pt(II)-Dithiolene Donor–Acceptor Charge-Transfer (CT) Systems: A Structural Analysis to Highlight DA Interactions
by Davide Espa, Luca Pilia, Flavia Artizzu, Angela Serpe, Paola Deplano and Luciano Marchiò
Molecules 2023, 28(6), 2566; https://doi.org/10.3390/molecules28062566 - 11 Mar 2023
Cited by 1 | Viewed by 1060
Abstract
The packing interactions of a series of electron donor (D) and electron acceptor (A) charge transfer (CT) near-IR absorbers based on platinum-dithiolene complexes are reinvestigated here as a case study also by using the Hirshfeld surface analysis. This analysis on systems, which exhibit [...] Read more.
The packing interactions of a series of electron donor (D) and electron acceptor (A) charge transfer (CT) near-IR absorbers based on platinum-dithiolene complexes are reinvestigated here as a case study also by using the Hirshfeld surface analysis. This analysis on systems, which exhibit the 1:1, 2:1 and 2:2 columnar stacking patterns between D and A, allows us to point out that several interactions of atoms and fragments are involved in the stacking interactions but also that only a limited fraction of these interactions, limited to the 1:1 D/A columnar stacking case, can be relatable to the absorption features of this class of compounds. Full article
(This article belongs to the Special Issue Metal Complexes for Optical and Electronics Applications)
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13 pages, 2549 KiB  
Article
Sulphur vs NH Group: Effects on the CO2 Electroreduction Capability of Phenylenediamine-Cp Cobalt Complexes
by Nicola Melis, Francesca Mocci, Annalisa Vacca and Luca Pilia
Molecules 2023, 28(5), 2364; https://doi.org/10.3390/molecules28052364 - 04 Mar 2023
Cited by 1 | Viewed by 1357
Abstract
The cobalt complex (I) with cyclopentadienyl and 2-aminothiophenolate ligands was investigated as a homogeneous catalyst for electrochemical CO2 reduction. By comparing its behavior with an analogous complex with the phenylenediamine (II), the effect of sulfur atom as a [...] Read more.
The cobalt complex (I) with cyclopentadienyl and 2-aminothiophenolate ligands was investigated as a homogeneous catalyst for electrochemical CO2 reduction. By comparing its behavior with an analogous complex with the phenylenediamine (II), the effect of sulfur atom as a substituent has been evaluated. As a result, a positive shift of the reduction potential and the reversibility of the corresponding redox process have been observed, also suggesting a higher stability of the compound with sulfur. Under anhydrous conditions, complex I showed a higher current enhancement in the presence of CO2 (9.41) in comparison with II (4.12). Moreover, the presence of only one -NH group in I explained the difference in the observed increases on the catalytic activity toward CO2 due to the presence of water, with current enhancements of 22.73 and 24.40 for I and II, respectively. DFT calculations confirmed the effect of sulfur on the lowering of the energy of the frontier orbitals of I, highlighted by electrochemical measurements. Furthermore, the condensed Fukui function f − values agreed very well with the current enhancement observed in the absence of water. Full article
(This article belongs to the Special Issue Metal Complexes for Optical and Electronics Applications)
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9 pages, 2603 KiB  
Article
Luminescent 1,10-Phenanthroline β-Diketonate Europium Complexes with Large Second-Order Nonlinear Optical Properties
by Francesco Fagnani, Alessia Colombo, Graziella Malandrino, Claudia Dragonetti and Anna Lucia Pellegrino
Molecules 2022, 27(20), 6990; https://doi.org/10.3390/molecules27206990 - 18 Oct 2022
Cited by 2 | Viewed by 1427
Abstract
Substitution of the diglyme ligand of [Eu(hfa)3(diglyme)] (where hfa is hexafluoroacetylacetonate) with a simple 1,10-phenanthroline leads to a six-fold increase of the product μβEFISH, as measured by the Electric-Field-Induced Second Harmonic generation (EFISH) technique. Similarly, [Eu(tta)3(1,10-phenanthroline)] (where [...] Read more.
Substitution of the diglyme ligand of [Eu(hfa)3(diglyme)] (where hfa is hexafluoroacetylacetonate) with a simple 1,10-phenanthroline leads to a six-fold increase of the product μβEFISH, as measured by the Electric-Field-Induced Second Harmonic generation (EFISH) technique. Similarly, [Eu(tta)3(1,10-phenanthroline)] (where Htta is 2-thenoyltrifluoroacetone) is characterized by a large second-order NLO response. Both 1,10-phenanthroline europium complexes have great potential as multifunctional materials for photonics. Full article
(This article belongs to the Special Issue Metal Complexes for Optical and Electronics Applications)
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15 pages, 2568 KiB  
Article
Photophysical and Primary Self-Referencing Thermometric Properties of Europium Hydrogen-Bonded Triazine Frameworks
by Chaoqing Yang, Dimitrije Mara, Joydeb Goura, Flavia Artizzu and Rik Van Deun
Molecules 2022, 27(19), 6687; https://doi.org/10.3390/molecules27196687 - 08 Oct 2022
Cited by 2 | Viewed by 1322
Abstract
Lanthanide hydrogen-bonded organic frameworks (LnHOFs) are recently emerging as a novel versatile class of multicomponent luminescent materials with promising potential applications in optics and photonics. Trivalent europium (Eu3+) incorporated polymeric hydrogen-bonded triazine frameworks (PHTF:Eu) have been successfully obtained via a facile [...] Read more.
Lanthanide hydrogen-bonded organic frameworks (LnHOFs) are recently emerging as a novel versatile class of multicomponent luminescent materials with promising potential applications in optics and photonics. Trivalent europium (Eu3+) incorporated polymeric hydrogen-bonded triazine frameworks (PHTF:Eu) have been successfully obtained via a facile and low-cost thermal pyrolysis route. The PHTF:Eu material shows a porous frame structure principally composed of isocyanuric acid and ammelide as a minor constituent. Intense red luminescence with high colour-purity from Eu3+ is obtained by exciting over a broad absorption band peaked at 300 nm either at room or low temperature. The triazine-based host works as excellent optical antenna towards Eu3+, yielding ~42% sensitization efficiency (ηsens) and an intrinsic quantum yield of Eu3+ emission (ΦEu) as high as ~46%. Temperature-dependent emission studies show that PHTF:Eu displays relatively high optical stability at elevated temperatures in comparison to traditional inorganic phosphors. The retrieved activation energy of 89 meV indicates that thermal quenching mechanisms are attributed to the intrinsic energy level structure of the metal-triazine assembly, possibly via a thermally activated back transfer to ligand triplet or CT states. Finally, by using an innovative approach based on excitation spectra, we demonstrate that PHTF:Eu can work as a universal primary self-referencing thermometer based on a single-emitting center with excellent relative sensitivity in the cryogenic temperature range. Full article
(This article belongs to the Special Issue Metal Complexes for Optical and Electronics Applications)
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9 pages, 2249 KiB  
Article
A Novel Class of Cyclometalated Platinum(II) Complexes for Solution-Processable OLEDs
by Dominique Roberto, Alessia Colombo, Claudia Dragonetti, Francesco Fagnani, Massimo Cocchi and Daniele Marinotto
Molecules 2022, 27(16), 5171; https://doi.org/10.3390/molecules27165171 - 13 Aug 2022
Cited by 4 | Viewed by 1613
Abstract
Substitution of the chlorido ligand of cyclometalated [Pt (5-R-1,3-di(2-pyridyl) benzene)Cl] (R = methyl, mesityl, 2-thienyl, or 4-diphenylamino-phenyl) by 4-phenylthiazole-2-thiolate leads to related thiolato complexes, which were fully characterized. Their photophysical properties were determined in degassed dichloromethane solution. The emission color of the novel [...] Read more.
Substitution of the chlorido ligand of cyclometalated [Pt (5-R-1,3-di(2-pyridyl) benzene)Cl] (R = methyl, mesityl, 2-thienyl, or 4-diphenylamino-phenyl) by 4-phenylthiazole-2-thiolate leads to related thiolato complexes, which were fully characterized. Their photophysical properties were determined in degassed dichloromethane solution. The emission color of the novel complexes can be easily tuned by the nature of the substituents on the terdentate ligand, as is the case for the parent chlorido complexes. Their luminescence Quantum Yield is high, with that of the compounds with the 2-thienyl or 4-diphenylamino-phenyl substituents being much higher than that of the related chloride complexes. The platinum complex with the cyclometalated 5-(2-thienyl)-1,3-di(2-pyridyl) benzene was used as the emitter for the fabrication of a yellow solution-processable OLED. Full article
(This article belongs to the Special Issue Metal Complexes for Optical and Electronics Applications)
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