Inorganics

Research

20 pages, 3224 KiB

Open AccessArticle

Pt(II) Complexes with a Novel Pincer N^C^N Ligand: Synthesis, Characterization, and Photophysics

by Evgeniia E. Luneva, Daria O. Kozina, Anna V. Mozzhukhina, Vitaly V. Porsev, Anastasia I. Solomatina and Sergey P. Tunik

Inorganics 2023, 11(5), 198; https://doi.org/10.3390/inorganics11050198 - 3 May 2023

Viewed by 2392

Abstract

A series of new platinum square planar complexes [Pt(NCN)L]^+/0 with the pincer N^C^N cyclometallated ligand (NC(H)N = 1,3-bis(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)benzene) containing the following L: Cl⁻, acetonitrile, pyridine, dimethylaminopyridine, 2,6-dimethylphenylisocyanide, has been synthesized. Application of bridging acetate ion as L ligand allowed [...] Read more.

A series of new platinum square planar complexes [Pt(NCN)L]^+/0 with the pincer N^C^N cyclometallated ligand (NC(H)N = 1,3-bis(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)benzene) containing the following L: Cl⁻, acetonitrile, pyridine, dimethylaminopyridine, 2,6-dimethylphenylisocyanide, has been synthesized. Application of bridging acetate ion as L ligand allowed obtaining a binuclear [Pt(NCN)]₂OOCCH₃ complex. The bulky and rigid structure of N^C^N-ligand provokes instability of its pincer coordination that makes possible transformation of the molecular architecture to give a heteronuclear complex with the Pt-Ag-Pt coordination core. The composition and structure of the obtained compounds were characterized in solution and in the solid state using ESI mass-spectrometry, NMR spectroscopy, elemental analysis, and single-crystal XRD crystallography. The complexes luminesce in solid state, solution, and in polymeric matrix demonstrating moderate to bright emission at ca. 550 nm with quantum yields up to 22% and lifetime of excited state up to 22 µs. TD DFT computational approach together with analysis of the photophysical properties in different media reveals the predominant ligand-centered ³IL nature of the radiative excited state localized at the N^C^N-ligand. The ancillary ligand L demonstrates a minor influence on the energy of emission but affects dramatically emission efficiency and lifetime. The chloride complex displays dual (fluorescence and phosphorescent) luminescence due to labile coordination of an N-coordinated functionality that produces a dangling aromatic fragment, which gives emission from a singlet excited state. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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10 pages, 4159 KiB

Open AccessArticle

Highly Sensitive and Highly Emissive Luminescent Thermometers for Elevated Temperatures Based on Lanthanide-Doped Polymers

by Liubov Tcelykh, Egor Latipov, Leonid Lepnev, Andrei Anosov, Vladislava Kozhevnikova, Natalia Kuzmina and Valentina V. Utochnikova

Inorganics 2023, 11(5), 189; https://doi.org/10.3390/inorganics11050189 - 27 Apr 2023

Cited by 2 | Viewed by 1694

Abstract

Lanthanide coordination compounds contining multiple lanthanides are the most promising candidate materials for luminescent thermometry. Sensing elevated temperatures requires highly stable complexes and matrices, such as those of thermally stable polymers. However, most high-temperature polymers are not optically inert, and this can affect [...] Read more.

Lanthanide coordination compounds contining multiple lanthanides are the most promising candidate materials for luminescent thermometry. Sensing elevated temperatures requires highly stable complexes and matrices, such as those of thermally stable polymers. However, most high-temperature polymers are not optically inert, and this can affect their thermometric properties, including decreasing their intensity and sensitivity. In the present paper, the proper selection of the combination of a matrix and two emitters allowed us to obtain a highly sensitive and highly emissive luminescent thermometry material, 1{5[Tb(Bz)₃Phen]₂+1[Eu(Bz)₃Phen]₂}:4PI4050, based on terbium and europium complexes in poly(ethylene glycol) diacrylate (PI4050), which is suitable for the detection of temperatures up to 200 °C. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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18 pages, 4825 KiB

Open AccessArticle

Luminescent Water-Dispersible Nanoparticles Engineered from Copper(I) Halide Cluster Core and P,N-Ligand with an Optimal Balance between Stability and ROS Generation

by Bulat A. Faizullin, Julia G. Elistratova, Igor D. Strelnik, Kamil D. Akhmadgaleev, Aidar T. Gubaidullin, Kirill V. Kholin, Irek R. Nizameev, Vasily M. Babaev, Syumbelya K. Amerhanova, Alexandra D. Voloshina, Tatiana P. Gerasimova, Andrey A. Karasik, Oleg G. Sinyashin and Asiya R. Mustafina

Inorganics 2023, 11(4), 141; https://doi.org/10.3390/inorganics11040141 - 26 Mar 2023

Cited by 3 | Viewed by 1655

Abstract

The present work introduces the solvent exchange procedure as a route for conversion of the Cu₄I₄L₂ complex, where the Cu₄I₄ cluster core is coordinated with two P,N-ligands (L), into an aqueous colloid. The analysis of [...] Read more.

The present work introduces the solvent exchange procedure as a route for conversion of the Cu₄I₄L₂ complex, where the Cu₄I₄ cluster core is coordinated with two P,N-ligands (L), into an aqueous colloid. The analysis of both colloidal and supernatant phases revealed some losses in CuI going from the initial Cu₄I₄L₂ complex to Cu₂I₂L₃-based nanoparticles. The comparative analysis of IR, ³¹P NMR spectroscopy, ESI mass-spectrometry and luminescence data argued for a contribution of the “butterfly”-like structures of the Cu₂I₂ cluster core to Cu₂I₂L₃-based nanoparticles, although the amorphous nature of the latter restricted structure evaluation from the PXRD data. The green luminescence of the colloids revealed their chemical stability under pH variations in the solutions of some amino acids and peptides, and to specify the temperature and concentration conditions triggering the oxidative degradation of the nanoparticles. The spin trap-facilitated ESR study indicated that the oxidative transformations were followed by the generation of reactive oxygen species (ROS). The physiological temperature level (310 K) enhanced the ROS generation by nanoparticles, but the ROS level was suppressed in the solution of GSH at pH = 7.0. The cytotoxicity of nanoparticles was evaluated in the M-HeLa cell line and is discussed in correlation with their cell internalization and intracellular oxidative transformations. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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13 pages, 2928 KiB

Open AccessArticle

Modeling the Eu(III)-to-Cr(III) Energy Transfer Rates in Luminescent Bimetallic Complexes

by Jorge A. A. Coelho, Renaldo T. Moura, Jr., Ricardo L. Longo, Oscar L. Malta and Albano N. Carneiro Neto

Inorganics 2023, 11(1), 38; https://doi.org/10.3390/inorganics11010038 - 10 Jan 2023

Cited by 4 | Viewed by 1904

Abstract

There is a growing interest in alternatives to lanthanide ion (Ln(III))-based luminescence sensitizing chromophores for in vivo applications, mainly in optical biological windows. Transition metals (M) are relevant candidates as chromophores as they have high absorption rates and emission bands covering a wide [...] Read more.

There is a growing interest in alternatives to lanthanide ion (Ln(III))-based luminescence sensitizing chromophores for in vivo applications, mainly in optical biological windows. Transition metals (M) are relevant candidates as chromophores as they have high absorption rates and emission bands covering a wide range of visible to near-infrared spectrum. However, despite the importance of theoretical models for the design of M–Ln(III) complexes, few contributions have devoted efforts to elucidating the energy transfer (ET) processes between M and Ln(III) ions. In this context, we adapted the intramolecular energy transfer (IET) to calculate, for the first time, the energy transfer rates for M–Ln(III) complexes. A new model was proposed that considers the assistance of phonons in the calculation of ET rates. As an example, the proposed model can estimate the ET rates between Eu(III) and Cr(III) ions in the [CrEuL₃]⁶⁺ complex (where L = 2-{6-[N,N-diethylcarboxamido]pyridin-2-yl}-1,1′-dimethyl-5,5′-methylene-2′-(5-methylpyridin-2-yl)bis [1H-benzimidazole]). The calculated rates (930–1200 s⁻¹) are in excellent agreement with the experimentally available data (750–1200 s⁻¹) when a phonon-assisted energy transfer process is considered. Thus, this proposed model can be useful to predict and explain photophysical properties driven by the energy transfer between Ln(III) ions and transition metals. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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10 pages, 2507 KiB

Open AccessArticle

Two-Dimensional and Three-Dimensional Coordination Polymers Based on Ln(III) and 2,5-Diiodoterephthalates: Structures and Luminescent Behavior

by Alexander S. Zaguzin, Mikhail A. Bondarenko, Pavel A. Abramov, Marianna I. Rakhmanova, Maxim N. Sokolov, Vladimir P. Fedin and Sergey A. Adonin

Inorganics 2022, 10(12), 262; https://doi.org/10.3390/inorganics10120262 - 16 Dec 2022

Cited by 5 | Viewed by 1880

Abstract

Five new coordination polymers based on Ln³⁺ and 2,5-diiodoterephthalates (2,5-I-bdc)— {[La₂(2,5-I-bdc)₃(DMF)₄]}·2DMF (1) and {[Ln₂(2,5-I-bdc)₃(DMF)₄]} (Ln = La (2), Nd (3), Sm (4) [...] Read more.

Five new coordination polymers based on Ln³⁺ and 2,5-diiodoterephthalates (2,5-I-bdc)— {[La₂(2,5-I-bdc)₃(DMF)₄]}·2DMF (1) and {[Ln₂(2,5-I-bdc)₃(DMF)₄]} (Ln = La (2), Nd (3), Sm (4) and Eu (5))—were prepared and characterized by single crystal and powder X-ray diffractometry. Luminescent behavior was examined (the highest quantum yield is 4.5%); thermal stability was examined using thermogravimetric analysis. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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19 pages, 5165 KiB

Open AccessArticle

Layered Gadolinium-Europium-Terbium Hydroxides Sensitised with 4-Sulfobenzoate as All Solid-State Luminescent Thermometers

by Anfisa A. Rodina, Alexey D. Yapryntsev, Bakhodur A. Abdusatorov, Ekaterina V. Belova, Alexander E. Baranchikov and Vladimir K. Ivanov

Inorganics 2022, 10(12), 233; https://doi.org/10.3390/inorganics10120233 - 1 Dec 2022

Cited by 2 | Viewed by 2604

Abstract

Ternary layered gadolinium-europium-terbium basic chlorides were synthesised using a facile hydrothermal-microwave technique. A continuous series of solid solutions was obtained in a full range of rare earth concentrations. To sensitise the luminescence of Eu³⁺ and Tb³⁺, a 4-sulfobenzoate anion was [...] Read more.

Ternary layered gadolinium-europium-terbium basic chlorides were synthesised using a facile hydrothermal-microwave technique. A continuous series of solid solutions was obtained in a full range of rare earth concentrations. To sensitise the luminescence of Eu³⁺ and Tb³⁺, a 4-sulfobenzoate anion was intercalated in the ternary layered rare earth hydroxides using one of two methods—a high-temperature ion exchange or a single-stage synthesis. The luminescent colour of the materials was governed by the gadolinium content: at low and medium gadolinium concentrations (0–70%), layered Gd-Eu-Tb basic sulfobenzoate exhibited a bright red europium luminescence; at high gadolinium content (70–90%), a bright green terbium luminescence was observed. The colour coordinates of layered Gd-Eu-Tb basic sulfobenzoate luminescence depended on the temperature in the physiological range (20–50 °C). The relative thermal sensitivity of the obtained materials was up to 2.9%·K⁻¹. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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11 pages, 2264 KiB

Open AccessArticle

Molecular and Supramolecular Structure of a New Luminescent Hybrid Compound: (C₅N₂H₁₄)₂[BiBr₆]Br·H₂O

by Andrey V. Bykov, Tatiana A. Shestimerova, Mikhail A. Bykov, Konstantin A. Lyssenko, Vladislav M. Korshunov, Mikhail T. Metlin, Ilya V. Taydakov and Andrei V. Shevelkov

Inorganics 2022, 10(11), 181; https://doi.org/10.3390/inorganics10110181 - 25 Oct 2022

Cited by 4 | Viewed by 2062

Abstract

The reaction of homopiperazine, C₅N₂H₁₂, with BiBr₃ in strong hydrobromic acid affords a new organic-inorganic hybrid (C₅N₂H₁₄)₂[BiBr₆]Br·H₂O. It crystallizes in the orthorhombic space group, [...] Read more.

The reaction of homopiperazine, C₅N₂H₁₂, with BiBr₃ in strong hydrobromic acid affords a new organic-inorganic hybrid (C₅N₂H₁₄)₂[BiBr₆]Br·H₂O. It crystallizes in the orthorhombic space group, Pbca, with unit cell dimensions of a = 15.0775 (2), b = 15.7569 (2), and c = 20.7881 (4) Å, and eight formula units per unit cell. The crystal structure features slightly distorted octahedral BiBr₆³⁻ and monoatomic Br⁻ anions in the inorganic substructure and C₅N₂H₁₄²⁺ dications and adjacent water molecules in the organic substructure. Various weak interactions that include (N)H···Br, (N)H···O, and (O)H···Br hydrogen bonds ensure the assembling of the structural moieties into a 3D supramolecular structure. (C₅N₂H₁₄)₂[BiBr₆]Br·H₂O shows two emission bands in the photoluminescence spectrum, a rather narrow deep-blue PL at 432 nm, and a broadband red PL centered at 650 nm. Their nature and relations to the crystal structure are discussed in this paper. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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13 pages, 3762 KiB

Open AccessArticle

Temperature-Sensitive Chameleon Luminescent Films Based on PMMA Doped with Europium(III) and Terbium(III) Anisometric Complexes

by Yuriy G. Galyametdinov, Aleksandr S. Krupin and Andrey A. Knyazev

Inorganics 2022, 10(7), 94; https://doi.org/10.3390/inorganics10070094 - 4 Jul 2022

Cited by 15 | Viewed by 2634

Abstract

The spin-coating technique was used to produce composite films consisting of PMMA polymer doped with anisometric complexes of Eu(III) and Tb(III). It was found that an increase in the content of Tb³⁺ complexes intensifies emission of both ions due to the intermolecular [...] Read more.

The spin-coating technique was used to produce composite films consisting of PMMA polymer doped with anisometric complexes of Eu(III) and Tb(III). It was found that an increase in the content of Tb³⁺ complexes intensifies emission of both ions due to the intermolecular energy transfer from the Tb(III) complex to the Eu(III) complex, which results in the increase in the relative luminescence quantum yield of Eu(III) ion by 36%. The temperature sensitivity of the film luminescence intensity and lifetime in the range of 296–363 K was investigated. The maximum relative sensitivity of the films reaches 5.44% × K⁻¹ and exceeds that of all known lanthanide-containing thermal sensors designed for measuring physiological temperatures. In combination with changing luminescence color, such a sensitivity makes these films promising colorimetric thermal sensors for in situ temperature measurements. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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