Inorganics

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16 pages, 4655 KiB

Open AccessArticle

Photophysical Properties of Eu³⁺ β-Diketonates with Extended π-Conjugation in the Aromatic Moiety

by Vladislav M. Korshunov, Alisia V. Tsorieva, Victoria E. Gontcharenko, Sergey R. Zanizdra, Mikhail T. Metlin, Trofim A. Polikovskiy and Ilya V. Taydakov

Inorganics 2023, 11(1), 15; https://doi.org/10.3390/inorganics11010015 - 28 Dec 2022

Cited by 5 | Viewed by 1584

Abstract

The influence of the degree of π-conjugation in biaroylmethane ligands upon Eu³⁺ luminescence efficiency in corresponding neutral tris-complexes was investigated in depth. The data obtained by both steady-state and time-resolved luminescence measurements gave an inside into electronic energy transfer mechanisms in the [...] Read more.

The influence of the degree of π-conjugation in biaroylmethane ligands upon Eu³⁺ luminescence efficiency in corresponding neutral tris-complexes was investigated in depth. The data obtained by both steady-state and time-resolved luminescence measurements gave an inside into electronic energy transfer mechanisms in the abovementioned complexes. It was shown that extension of the π-system in the naphthalene moiety in comparison to the phenyl one lead to a substantial decrease of both the S₁ and T₁ energy of the corresponding symmetrical β-diketones, which, in turn, led to a decrease of the total quantum yield of respective Eu³⁺ complexes. The obtained results are of interest for the rational design of highly luminescent complexes with NIR-emitting lanthanides, as the resonant levels energies are low and can hardly be sensitized by common ligands. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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12 pages, 4959 KiB

Open AccessArticle

Manganese(II) Bromide Compound with Diprotonated 1-Hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydrobenzimidazole: Dual Emission and the Effect of Proton Transfers

by Alexey S. Berezin, Boris Selivanov, Andrey Danilenko, Aleksandr Sukhikh and Andrey Komarovskikh

Inorganics 2022, 10(12), 245; https://doi.org/10.3390/inorganics10120245 - 06 Dec 2022

Cited by 7 | Viewed by 1487

Abstract

An organic–inorganic cation–anion manganese(II) tetrabromide compound with diprotonated 1-hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydrobenzimidazole, [H₃L][MnBr₄][H₂O], has been synthesized and investigated. The compound has a few possible pathways for proton transfers, which play an important role in the observed luminescence, optical, and magnetic [...] Read more.

An organic–inorganic cation–anion manganese(II) tetrabromide compound with diprotonated 1-hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydrobenzimidazole, [H₃L][MnBr₄][H₂O], has been synthesized and investigated. The compound has a few possible pathways for proton transfers, which play an important role in the observed luminescence, optical, and magnetic properties. The proton transfers result in the appearance of two-band luminescence. One band is caused by the Mn(II) d-d transitions. The other band is caused by the transition from the triplet state of organic cation and the d-d transition of manganese(II) coupled through {[H₃L]}-{[MnBr₄]}-{[H₂O]} vibrations. The optical absorption spectra of [H₃L][MnBr₄][H₂O] indicate the presence of two direct and one indirect band transitions. The reason for the two-band luminescence and complex optical absorption in [H₃L][MnBr₄][H₂O] were additionally considered using the DFT calculations. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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14 pages, 2111 KiB

Open AccessArticle

Composites Based on Polylactide Doped with Amorphous Europium(III) Complex as Perspective Thermosensitive Luminescent Materials

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

Inorganics 2022, 10(12), 232; https://doi.org/10.3390/inorganics10120232 - 30 Nov 2022

Viewed by 1409

Abstract

This work reports fabrication of polylactide (PLA) films doped with various additives of an amorphous Eu(III) complex. We study the temperature behavior of the luminescence intensity and lifetime of the PLA-Eu(III) composites in the range of 298–353 K and investigate the mechanism of [...] Read more.

This work reports fabrication of polylactide (PLA) films doped with various additives of an amorphous Eu(III) complex. We study the temperature behavior of the luminescence intensity and lifetime of the PLA-Eu(III) composites in the range of 298–353 K and investigate the mechanism of luminescence temperature quenching. The peak relative sensitivity of the films reaches 20.1 %×K⁻¹ and exceeds the respective characteristics of all known lanthanide-containing thermosensors designed for the range of physiological temperatures. The produced films can be potential novel materials for luminescent thermosensors. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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13 pages, 4628 KiB

Open AccessArticle

Stabilization of {Ag₂₀(S^tBu)₁₀} and {Ag₁₉(S^tBu)₁₀} Toroidal Complexes in DMSO: HPLC-ICP-AES, PL, and Structural Studies

by Victoria V. Volchek, Alexey S. Berezin, Maxim N. Sokolov and Pavel A. Abramov

Inorganics 2022, 10(12), 225; https://doi.org/10.3390/inorganics10120225 - 26 Nov 2022

Cited by 1 | Viewed by 1169

Abstract

The presence of DMSO provides a unique ability to stabilize silver toroidal complexes in the direct reaction between AgS^tBu and AgNO₃ at 80 °C. Slow cooling results in large crystals of [NO₃@Ag_19.2(S^tBu)₁₀(DMSO) [...] Read more.

The presence of DMSO provides a unique ability to stabilize silver toroidal complexes in the direct reaction between AgS^tBu and AgNO₃ at 80 °C. Slow cooling results in large crystals of [NO₃@Ag_19.2(S^tBu)₁₀(DMSO)_5.2(NO₃)_8.2]·3DMSO (1), which were isolated and characterized by single crystal X-ray diffraction (SCXRD) analysis. The crystal structure contains both {Ag₂₀(S^tBu)₁₀} and {Ag₁₉(S^tBu)₁₀} clusters. The solution of these material in DMSO was studied with HPLC techniques, which demonstrated the presence of both complexes in solution. The use of [SiW₁₂O₄₀]^4– as counter anion gives crystals of a double complex salt [Ag_17.8(NO₃)_3.8(S^tBu)₁₀][SiW₁₂O₄₀]·30DMSO (2) under the same conditions. Temperature-dependent photoluminescence (PL) was studied. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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12 pages, 2583 KiB

Open AccessArticle

Aurophilic Interactions of Dimeric Bisphosphine Gold(I) Complexes Pre-Organized by the Structure of the 1,5-Diaza-3,7-Diphosphacyclooctanes

by Irina R. Dayanova, Adelina I. Fayezova, Igor D. Strelnik, Igor A. Litvinov, Daut R. Islamov, Ilya E. Kolesnikov, Tatiana P. Gerasimova, Elvira I. Musina and Andrey A. Karasik

Inorganics 2022, 10(12), 224; https://doi.org/10.3390/inorganics10120224 - 25 Nov 2022

Cited by 2 | Viewed by 1114

Abstract

The dimeric gold(I) chloride and gold(I) iodide complexes ([L₂Au]Cl₂ and L₂AuI₂) on the scaffold of the cyclic bisphosphine, namely 1,5-diaza-3,7-diphosphacyclooctane containing α-phenylbenzyl (benzhydryl) substituents at the nitrogen atoms, were synthesized. The obtained complexes were isolated as [...] Read more.

The dimeric gold(I) chloride and gold(I) iodide complexes ([L₂Au]Cl₂ and L₂AuI₂) on the scaffold of the cyclic bisphosphine, namely 1,5-diaza-3,7-diphosphacyclooctane containing α-phenylbenzyl (benzhydryl) substituents at the nitrogen atoms, were synthesized. The obtained complexes were isolated as white crystalline powders. The single crystal XRD of the obtained complexes revealed the strong aurophilic interactions between two gold(I) atoms with the Au^…Au distance values of 2.9977(6) and 3.1680(5) Å. The comparison of the gold complexes, based on the N,N-diaryl- and N,N-dibenzhydryl substituted 1,5-diaza-3,7-diphosphacyclooctanes, allowed to reveal the strong impact of the initial heterocycle conformation on the realization of the aurophilic interactions, where the geometry of N,N-dibenzhydryl substituted 1,5-diaza-3,7-diphosphacyclooctane, is pre-organized for the intramolecular aurophilic interactions of the complexes. The obtained complexes exhibit a bluish-green phosphorescence (λ_em 505 (-Cl) and 530(-I)) in the solid state at room temperature, originated by the metal-halide centered transitions, which was confirmed by the TDDFT calculations. It was found that the aurophilic interactions are realized in the ground and in the triplet excited states of the complexes. The slighter change of the geometry of the N,N-dibenzhydryl substituted gold(I) iodide complexes, under the transition from the ground state to the excited state, in comparison with their N,N-diaryl substituted analogues, results in the reduced values of the Stokes shift of luminescence (ca. 150 nm vs. 175 nm). Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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16 pages, 3694 KiB

Open AccessArticle

Synthesis, Structure and Photoluminescence Properties of Cd and Cd-Ln Pentafluorobenzoates with 2,2′:6′,2′-Terpyridine Derivatives

by Maxim A. Shmelev, Julia K. Voronina, Maxim A. Evtyukhin, Fedor M. Dolgushin, Evgenia A. Varaksina, Ilya V. Taydakov, Aleksey A. Sidorov, Igor L. Eremenko and Mikhail A. Kiskin

Inorganics 2022, 10(11), 194; https://doi.org/10.3390/inorganics10110194 - 01 Nov 2022

Cited by 7 | Viewed by 1797

Abstract

Six new complexes [Cd(tpy)(pfb)₂] (1, tpy = 2,2′:6′,2″-terpyridine), [Ln₂Cd₂(tpy)₂(pfb)₁₀] (Ln = Eu (2_Eu), Tb (2_Tb)), [Ln₂Cd₂(tbtpy)₂(pfb)₁₀]·2MeCN (Ln = Eu (3_Eu [...] Read more.

Six new complexes [Cd(tpy)(pfb)₂] (1, tpy = 2,2′:6′,2″-terpyridine), [Ln₂Cd₂(tpy)₂(pfb)₁₀] (Ln = Eu (2_Eu), Tb (2_Tb)), [Ln₂Cd₂(tbtpy)₂(pfb)₁₀]·2MeCN (Ln = Eu (3_Eu), Tb (3_Tb), tbtpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine), [Eu₂Cd₂(tppz)(pfb)₁₀]n (4, tppz = 2,3,5,6-tetra-(pyridin-2-yl)pyrazine) based on pentafluorobenzoic acid (Hpfb) have been prepared and investigated. The effect of tridentate ligands on geometry heterometallic scaffolds synthesized complexes is discussed. The supramolecular crystal structures of the new compounds are stabilized by π-π, C-F···π, C-H···O, C-H...F, F….F interactions. Non-covalent interactions have been studied using Hirschfeld surface analysis. The obtained compounds were characterized by single-crystal and powder X-ray diffraction, luminescence spectroscopy, IR spectroscopy, CHN analysis. Complexes 2_Ln and 3_Ln exhibit metal-centered photoluminescence, but the presence of ligand luminescence bands indicates incomplete energy transfer from the d-block to the lanthanide ion. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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13 pages, 2410 KiB

Open AccessArticle

Aliphatic-Bridged Early Lanthanide Metal–Organic Frameworks: Topological Polymorphism and Excitation-Dependent Luminescence

by Pavel A. Demakov, Alexey A. Ryadun and Vladimir P. Fedin

Inorganics 2022, 10(10), 163; https://doi.org/10.3390/inorganics10100163 - 01 Oct 2022

Cited by 6 | Viewed by 1716

Abstract

Six new three-dimensional metal–organic frameworks based on early lanthanide(III) cations and trans-1,4-cyclohexanedicarboxylic acid (H₂chdc) were obtained. Their crystal structures were determined by single-crystal X-ray diffraction analysis. The structure of [La₂(H₂O)₄(chdc)₃]·2DMF·H₂O [...] Read more.

Six new three-dimensional metal–organic frameworks based on early lanthanide(III) cations and trans-1,4-cyclohexanedicarboxylic acid (H₂chdc) were obtained. Their crystal structures were determined by single-crystal X-ray diffraction analysis. The structure of [La₂(H₂O)₄(chdc)₃]·2DMF·H₂O (1; DMF = N,N-dimethylformamide) contains one-dimensional infinite La(III)-carboxylate chains interconnected by cyclohexane moieties to form a highly porous polymeric lattice with 30% solvent accessible volume. Compounds [Ln₂(phen)₂(chdc)₃]·0.75DMF (2_Ln; Ln³⁺ = Ce³⁺, Pr³⁺, Nd³⁺ and Sm³⁺; phen = 1,10-phenanthroline) are based on binuclear carboxylate building blocks, which are decorated by chelate phenanthroline ligands and interconnected by cyclohexane moieties to form more dense isostructural coordination frameworks with primitive cubic pcu topology. Compound [Nd₂(phen)₂(chdc)₃]·2DMF·0.67H₂O (3) is based on secondary building units similar to 2_Ln and contains a coordination lattice isomeric to 2_Ln with a rare hexagonal helical snz topology. Thermal stability and luminescent properties were investigated. For 2_Sm, a strong and nonmonotonous dependence of the luminescence color on the variation of excitation wavelength was revealed, changing its emission from pinkish red at λ_ex = 340 nm to white at λ_ex = 400 nm, and then to yellow at lower excitation energies. Such nonlinear behavior was rationalized in terms of the contribution of several different luminescence mechanisms. Thus, 2_Sm is a rather rare example of a highly tunable monometallic lanthanide-based luminophore with possible applications in light-emitting devices and optical data processing. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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10 pages, 2022 KiB

Open AccessArticle

Luminescent Zn Halide Complexes with 2-(2-Aminophenyl)benzothiazole Derivatives

by Taisiya S. Sukhikh, Dmitry S. Kolybalov, Ekaterina K. Pylova and Sergey N. Konchenko

Inorganics 2022, 10(9), 138; https://doi.org/10.3390/inorganics10090138 - 15 Sep 2022

Cited by 4 | Viewed by 1399

Abstract

We report a comparative study of coordination behaviour of 2-(2-aminophenyl)benzothiazole (NH₂-pbt) and its phosphorus-containing derivative, α-aminophosphine oxide (PCNH-pbt), towards zinc halides. The corresponding coordination compounds [Zn(L)₂Hal₂] (L = PCNH-pbt, Hal = [...] Read more.

We report a comparative study of coordination behaviour of 2-(2-aminophenyl)benzothiazole (NH₂-pbt) and its phosphorus-containing derivative, α-aminophosphine oxide (PCNH-pbt), towards zinc halides. The corresponding coordination compounds [Zn(L)₂Hal₂] (L = PCNH-pbt, Hal = Cl, 1 and Hal = Br, 2) and [Zn(L’)Hal₂] (L’ = NH₂-pbt, Hal = Cl, 3 and Hal = Br, 4) were obtained as single phases. As evidenced by single-crystal X-ray diffraction analysis, L’ ligand coordinates to Zn in a chelate manner via two N atoms. Despite a similar coordination mode in complexes 3 and 4, the spatial geometry of the ligand differs notably, which implies a relatively high flexibility of NH₂-pbt. The L ligand exhibits another coordination mode, binding with Zn only via the oxygen of the P=O group. The differences in the structures of NH₂-pbt, 3 and 4, and their counterparts, PCNH-pbt, 1 and 2, induce differences in their solid-state photoluminescence properties. The former group of the compounds exhibits conventional single-band emission, while the latter group reveals two bands. The minor band at 450 nm is ascribed to a radiative transition for the regular amine species, while the major band at 520–550 nm can be associated either with the proton-transferred imine species (ESIPT mechanism) or with a charge transfer state (TICT) with a different geometry. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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17 pages, 8959 KiB

Open AccessArticle

New Carboxylate Anionic Sm-MOF: Synthesis, Structure and Effect of the Isomorphic Substitution of Sm³⁺ with Gd³⁺ and Tb³⁺ Ions on the Luminescent Properties

by Anna A. Ivanova, Victoria E. Gontcharenko, Alexey M. Lunev, Anastasia V. Sidoruk, Ilya A. Arkhipov, Ilya V. Taydakov and Yuriy A. Belousov

Inorganics 2022, 10(8), 104; https://doi.org/10.3390/inorganics10080104 - 25 Jul 2022

Cited by 8 | Viewed by 2824

Abstract

Two new compounds, namely {(NMe₂H₂)}[Ln(TDA)(HCOO)] 0.5H₂O, Ln = Sm³⁺ (Sm-TDA) and Gd³⁺ (Gd-TDA), where TDA³⁻ is the anion of 1H-1,2,3-triazole-4,5-dicarboxylic acid (H₃TDA), were synthesized by the [...] Read more.

Two new compounds, namely {(NMe₂H₂)}[Ln(TDA)(HCOO)] 0.5H₂O, Ln = Sm³⁺ (Sm-TDA) and Gd³⁺ (Gd-TDA), where TDA³⁻ is the anion of 1H-1,2,3-triazole-4,5-dicarboxylic acid (H₃TDA), were synthesized by the solvothermal method in a DMF:H₂O mixture. According to single-crystal X-ray diffraction data, the compounds are 3d-MOFs with an anionic lattice and dimethylammonium cations occupying part of the cavities. Based on these compounds, two series of mixed-metal complexes, [NMe₂H₂][Sm_xLn_1-x(TDA)(HCOO)], (x = 0.9 (Sm_0.9Ln_0.1-TDA), x = 0.8 (Sm_0.8-Ln_0.2-TDA)…Sm_0.02Ln_0.98-TDA, Ln = Tb, Gd), were also obtained and characterized by powder XRD. The luminescent properties of the compounds were studied and it was shown that the resulting compounds are two- or three-component emitters with the possibility of fine color tuning by changing the intensities of fluorescence and phosphorescence of the ligand, as well as the luminescence of Sm³⁺ and Tb³⁺ f-ions. Full article

(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)

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