Multifunctionality of luminescent molecular nanomagnets based on lanthanide complexes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(40), P. 5961 - 5986

Published: Jan. 1, 2023

Multifunctional materials, which exhibit diverse physical properties, are candidates for the new generation of smart devices that realize many tasks simultaneously. Particular attention is given to single-phase multifunctional materials offer effects induced by coupling between introduced properties. Complexes lanthanide(3+) ions an attractive source multifunctionality since they combine luminescent functionalities related their f-f or d-f electronic transitions with magnetic anisotropy originates from spin-orbit and crystal-field effects. The resulting single-molecule magnets (SMMs) link area functional luminophores, applicable in light-emitting diodes sensing, field molecular magnets, high-density data storage, additional advantages, e.g., fruitful magneto-optical correlations switching emission a field. It was recently shown lanthanide SMMs can provide richly expanded towards sensitivity solvent exchange, temperature, light, as well electrical such super-ionic conductivity ferroelectricity, non-centrosymmetricity- chirality-related effects, second-harmonic circularly polarized luminescence. Here, we discuss pioneering reports on use SMMs, emphasis our contribution relying functionalization 4f metal complexes through insertion into heterometallic coordination compounds.

Language: Английский

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Impacts of β-Diketonate Terminal Ligands on Slow Magnetic Relaxation and Luminescence Thermometry in Dinuclear DyIII Single-Molecule Magnets Leveraging Subtle Local Coordination Modifications to Refine the Slow Relaxation of Magnetization and Enhance Luminescence Thermometry in Dinuclear DyIII Single-Molecule Magnets

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Influence of coordination environment and electronic structure on slow magnetic relaxation luminescent thermometry dinuclear Dy III SMMs with optical properties.

Language: Английский

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Multifunctional lanthanide-based single-molecule magnets exhibiting luminescence thermometry and photochromic and ferroelectric properties

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(15), P. 4643 - 4657

Published: Jan. 1, 2023

We review the recent research progress of multifunctional lanthanide-based single-molecule magnets exhibiting luminescence thermometry and photochromic ferroelectric properties, as well synergistic effect between them.

Language: Английский

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ZnTe Crystal Multimode Cryogenic Thermometry Using Raman and Luminescence Spectroscopy

Materials, Journal Year: 2023, Volume and Issue: 16(3), P. 1311 - 1311

Published: Feb. 3, 2023

In this study, ZnTe crystal was applied to provide precise thermal sensing for cryogenic temperatures. Multiple techniques, namely Raman and photoluminescence spectroscopies, were used broaden the operating temperature range improve reliability of proposed thermometers. Raman-based could be in 20-100 K, while luminescence-based thermometry utilized a narrower 20-70 K. However, latter strategy provides better relative sensitivity resolution. The best performances based on single temperature-dependent parameter attain Sr = 3.82% K-1 ΔT 0.12 K at T 50 synergy between multiple linear regression multiparametric demonstrated results ten-fold improvement two-fold enhancement ΔT. All studies performed testify that is promising multimode contactless optical sensor thermometry.

Language: Английский

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Multifunctional lanthanide(III) single-molecule magnets displaying luminescence thermometry: Progress, challenges, and future directions

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 537, P. 216685 - 216685

Published: April 15, 2025

Language: Английский

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Toward Magneto‐Optical Cryogenic Thermometers with High Sensitivity: A Magnetic Circular Dichroism Based Thermometric Approach

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 19, 2023

Abstract Remote temperature probing at the cryogenic range is of utmost importance for advancement future quantum technologies. Despite notable achievements in luminescent thermometers, accurately measuring temperatures below 10 K remains a challenging endeavor. In this study, we propose novel magneto‐optical thermometric approach based on magnetic‐circular dichroism (MCD) technique, which offers unprecedented capabilities meticulous variation analysis temperatures. The inherent sensitivity MCD C ‐term, conjunction with both positive and negative signals, enables highly sensitive probing. Additionally, groundbreaking relative thermal value 95.3 % −1 2.54 can be achieved using mononuclear lanthanide complex, [[Ho(acac) 3 (phen)], presence 0.25 T applied magnetic field combination multiparametric read‐out multiple regression. These results unequivocally demonstrate viability effectiveness our methodology sensing.

Language: Английский

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Tuning of Ratiometric Optical Thermometry in the Family of Magnetic {Nd_1–x^IIIYb^III_x[Cu₂^I(CN)₅]} Frameworks Showing the Large SHG Response

The Journal of Physical Chemistry C, Journal Year: 2023, Volume and Issue: 127(31), P. 15500 - 15511

Published: July 27, 2023

Three-dimensional (3-D) coordination networks provide a stable framework preferable to designing materials with tunable properties by various chemical modifications, such as solvent exchange, element doping, etc. In this work, we explored extensively the 3-D cyanido-bridged heterometallic assemblies having Nd(III) and Yb(III) centers in combination polycyanidocuprate(I) ions, that is, family of [Nd1–xIIIYbIIIx(2,2′-bpdo)2(H2O)][Cu2I(CN)5]·5H2O (x = 0, 0.25, 0.5, 0.75, 1 (1–5); 2,2′-bpdo 2,2′-bipyridine N,N′-dioxide) networks. To form lanthanide-incorporating molecule-based matrix, two different types cuprate(I) moieties are spontaneously formed during crystallization, resulting trigonal planar tricyanido tetrahedral tetracyanidocopper(I)-based molecular anions. 1–5 exhibit optical thermometry based on near-infrared (NIR) luminescence. The relative thermal sensitivity Nd(III)-containing is considerably improved through preparation analogous mixed compounds introducing Yb3+ which also enables tunability over operating temperature range. Since all crystallize within non-centrosymmetric Cc space group, they second-harmonic generation (SHG) phenomenon, signal highest among metal (the SHG efficiency ∼120% reference potassium dihydrogen phosphate). Furthermore, show field-induced single-molecule magnet (SMM) behavior related lanthanide(3+) slow magnetic relaxation occurring via Raman direct processes.

Language: Английский

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Temperature Dependence of Coherent versus Spontaneous Raman Scattering

Physical Review Letters, Journal Year: 2024, Volume and Issue: 133(20)

Published: Nov. 15, 2024

Because of their sub picosecond temporal resolution, coherent Raman spectroscopies have been proposed as a viable extension spontaneous thermometry, to determine dynamics mode specific vibrational energy content during out equilibrium molecular processes. Here we show that the presence multiple laser fields stimulating coherences introduces additional quantum pathways, resulting in destructive interference. This ultimately reduces thermal sensitivity single spectral lines, nullifying it for harmonic vibrations and temperature independent polarizability. We demonstrate how harnessing anharmonic signatures such hot bands enables thermometry.

Language: Английский

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Thermometric Properties of Thio/Selenocyanato-Bridged Spin-Crossover Networks

Chemistry of Materials, Journal Year: 2023, Volume and Issue: 35(22), P. 9613 - 9622

Published: Nov. 11, 2023

Thermometry is a well-researched topic in materials science, but recent advances multifunctional complexes have introduced the idea of highly sensitive and accurate contact or noncontact thermometers, which utilize temperature-dependent evolution physical properties. In this context, {[Fe(μ-pyrazine)2][Fe(MeOH)2][Hg(μ-ECN)3(ECN)]2}·2H2O (E = S, FeHgS, E Se, FeHgSe) three-dimensional networks with spin-transition temperature T1/2 191 K were considered promising materials. Temperature-dependent UV–visible–NIR, IR, Raman spectra displayed strong dependence on peak intensities positions temperature. Subsequently, first-principles calculations for low- high-spin states gave thorough description spectroscopic properties origins. The unique variability caused by combination gradual spin-crossover (SCO)-active Fe centers SCO-inactive as reference allowed us to prove feasibility thermometric concept via characterization UV–vis–NIR, intensity ratios. particular, compared UV–vis–NIR absorption thermometry, IR thermometry manifested high thermal sensitivity (Sr) best values 3.2% K–1 at 182 (FeHgS, IR), 3.1% 131 (FeHgSe, 16.3% 184 Raman), 12.1% 186 Raman). Overall, realization optical vibrational SCO thermometers has significant implications practical application switchable leads development advanced thermometers.

Language: Английский

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Nonlinear and Emissive {[M^III(CN)₆]^3–···Polyresorcinol} (M = Fe, Co, Cr) Cocrystals Exhibiting an Ultralow Frequency Raman Response

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 63(4), P. 1803 - 1815

Published: Dec. 18, 2023

Optically active functional noncentrosymmetric architectures might be achieved through the combination of molecules with inscribed optical responses and species dedicated tectonic character. Herein, we present new series cocrystal salt solvates (PPh4)3[M(CN)6](L)n·msolv (M = Cr(III), Fe(III), Co(III); L polyresorcinol coformers, multiple hydrogen bond donors: 3,3′,5,5′-tetrahydroxy-1,19-biphenyl, DiR, n 2, or 5′-(3,5-dihydroxyphenyl)-3,3″,5,5″-tetrahydroxy-1,19:3′,1″-terphenyl, TriRB, 1) denoted as MDiR MTriRB, respectively. The hydrogen-bonded subnetworks {[M(CN)6]3–;Ln}∞ dmp, neb, dia topology are formed structural matching between building blocks within supramolecular cis-bis(chelate)-like {[M(CN)6]3–;(H2L)2(HL)2} tris(chelate)-like {[M(CN)6]3–;(H2L)3} fragments. quantum-chemical analysis demonstrates mixed electrostatic covalent character these interactions, their strength clearly enhanced due to negative charge acceptor metal complex. corresponding interaction energy is also dependent on geometry contact size its components, rotational degree freedom extent π-electron system coformer, overall fit molecular surroundings. Symmetry crystal lattices correlated local symmetry coformers {complex;(coformer)n} motifs characterized by absence inversion center mirror plane. All compounds reveal second-harmonic generation activity photoluminescence diversified individual UV–vis spectral characteristics interesting low-frequency Raman scattering spectra subterahertz spectroscopic domain. Vibrational (infrared/Raman), electronic absorption (experimental calculated), 57Fe Mössbauer together electrospray ionization mass spectrometry (ESI-MS) data provided for complete description our systems.

Language: Английский

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