magnetic properties of excited states Dotaz Zobrazit nápovědu
Systematic scrutiny is carried out of the ability of multicentre bond indices and the NOEL-based similarity index dAB to serve as excited-state aromaticity criteria. These indices were calculated using state-optimized complete active-space self-consistent field wavefunctions for several low-lying singlet and triplet states of the paradigmatic molecules of benzene and square cyclobutadiene and the inorganic ring S2N2. The comparison of the excited-state indices with aromaticity trends for individual excited states suggested by the values of magnetic aromaticity criteria show that whereas the indices work well for aromaticity reversals between the ground singlet and first triplet electronic states, addressed by Baird's rule, there are no straightforward parallels between the two sets of data for singlet excited states. The problems experienced while applying multicentre bond indices and dAB to singlet excited states are explained by the loss of the information inherently present in wavefunctions and/or pair densities when calculating the first-order density matrix.
- Klíčová slova
- excited-state aromaticity reversals, magnetic properties of excited states, molecular similarity, multicentre bond indices,
- MeSH
- benzen chemie MeSH
- butadieny chemie MeSH
- elektrony MeSH
- kvantová teorie MeSH
- molekulární modely MeSH
- molekulární struktura * MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- 1,3-butadiene MeSH Prohlížeč
- benzen MeSH
- butadieny MeSH
Magnetic Raman optical activity of gases provides unique information about their electric and magnetic properties. Magnetic Raman optical activity has recently been observed in a paramagnetic gas (Angew. Chem. Int. Ed. 2012, 51, 11058; Angew. Chem. 2012, 124, 11220). In diamagnetic molecules, it has been considered too weak to be measurable. However, in chlorine, bromine and iodine vapors, we could detect a significant signal as well. Zeeman splitting of electronic ground-state energy levels cannot rationalize the observed circular intensity difference (CID) values of about 10(-4). These are explicable by participation of paramagnetic excited electronic states. Then a simple model including one electronic excited state provides reasonable spectral intensities. The results suggest that this kind of scattering by diamagnetic molecules is a general event observable under resonance conditions. The phenomenon sheds new light on the role of excited states in the Raman scattering, and may be used to probe molecular geometry and electronic structure.
- Klíčová slova
- Raman optical activity, angular momentum theory, diamagnetic molecules, excited electronic states, magnetic field,
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
Novel Yb,Tb,Nd-doped GdF3 and NaGdF4 nanoparticles were synthesized by a coprecipitation method in ethylene glycol (EG) in the presence of the poly(4-styrenesulfonic acid-co-maleic anhydride) stabilizer. The particle size and morphology, crystal structure, and phase change were controlled by adjusting the PSSMA concentration and source of fluoride anions in the reaction. Doping of Yb3+, Tb3+, and Nd3+ ions in the NaGdF4 host nanoparticles induced luminescence under ultraviolet and near-infrared excitation and high relaxivity in magnetic resonance (MR) imaging (MRI). In vitro toxicity of the nanoparticles and their cellular uptake efficiency were determined in model rat pancreatic β-cells (INS-1E). As the NaGdF4:Yb,Tb,Nd@PSSMA-EG nanoparticles were non-toxic and possessed good luminescence and magnetic properties, they were applicable for in vitro optical and MRI of isolated pancreatic islets in phantoms. The superior contrast was achieved for in vivo T2*-weighted MR images of the islets transplanted under the kidney capsule to mice in preclinical trials.
- Klíčová slova
- MRI, gadolinium fluoride, luminescence, nanoparticles, pancreatic islets, β-cells,
- MeSH
- krysa rodu Rattus MeSH
- Langerhansovy ostrůvky * diagnostické zobrazování MeSH
- luminiscence MeSH
- magnetická rezonanční tomografie metody MeSH
- maleinanhydridy MeSH
- myši MeSH
- nanočástice * chemie MeSH
- zvířata MeSH
- Check Tag
- krysa rodu Rattus MeSH
- myši MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- maleinanhydridy MeSH
The present work focuses on the hydrothermal synthesis and properties of porous coordination polymers of metal-porphyrin framework (MPF) type, namely, {[Pr4(H2TPPS)3]·11H2O} n (UPJS-10), {[Eu/Sm(H2TPPS)]·H3O+·16H2O} n (UPJS-11), and {[Ce4(H2TPPS)3]·11H2O} n (UPJS-12) (H2TPPS = 4,4',4″,4‴-(porphyrin-5,10,15,20-tetrayl)tetrakisbenzenesulfonate(4-)). The compounds were characterized using several analytical techniques: infrared spectroscopy, thermogravimetric measurements, elemental analysis, gas adsorption measurements, and single-crystal structure analysis (SXRD). The results of SXRD revealed a three-dimensional open porous framework containing crossing cavities propagating along all crystallographic axes. Coordination of H2TPPS4- ligands with Ln(III) ions leads to the formation of 1D polymeric chains propagating along the c crystallographic axis. Argon sorption measurements at -186 °C show that the activated MPFs have apparent BET surface areas of 260 m2 g-1 (UPJS-10) and 230 m2 g-1 (UPJS-12). Carbon dioxide adsorption isotherms at 0 °C show adsorption capacities up to 1 bar of 9.8 wt % for UPJS-10 and 8.6 wt % for UPJS-12. At a temperature of 20 °C, the respective CO2 adsorption capacities decreased to 6.95 and 5.99 wt %, respectively. The magnetic properties of UPJS-10 are characterized by the presence of a close-lying nonmagnetic ground singlet and excited doublet states in the electronic spectrum of Pr(III) ions. A much larger energy difference was suggested between the two lowest Kramers doublets of Ce(III) ions in UPJS-12. Finally, the analysis of X-band EPR spectra revealed the presence of radical spins, which were tentatively assigned to be originating from the porphyrin ligands.
- Publikační typ
- časopisecké články MeSH
The design of four new fluorinated biaryl fluorescent labels and their attachment to nucleosides and nucleoside triphosphates (dNTPs) by the aqueous cross-coupling reactions of biarylboronates is reported. The modified dNTPs were good substrates for KOD XL polymerase and were enzymatically incorporated into DNA probes. The photophysical properties of the biaryl-modified nucleosides, dNTPs, and DNA were studied systematically. The different substitution pattern of the biaryls was used for tuning of emission maxima in the broad range of 366-565 nm. Using methods of computational chemistry the emission maxima were reproduced with a satisfactory degree of accuracy, and it was shown that the large solvatochromic shifts observed for the studied probes are proportional to the differences in dipole moments of the ground (S(0)) and excited (S(1)) states that add on top of smaller shifts predicted already for these systems in vacuo. Thus, we present a set of compounds that may serve as multipurpose base-discriminating fluorophores for sensing of hairpins, deletions, and mismatches by the change of emission maxima and intensities of fluorescence and that can be also conviently studied by (19)F NMR spectroscopy. In addition, aminobenzoxazolyl-fluorophenyl-labeled nucleotides and DNA also exert dual pH-sensitive and solvatochromic fluorescence, which may imply diverse applications.
- MeSH
- DNA sondy chemická syntéza chemie MeSH
- DNA-dependentní DNA-polymerasy chemie MeSH
- fluor chemie MeSH
- fluorescenční barviva chemická syntéza chemie MeSH
- fluorescenční spektrometrie MeSH
- koncentrace vodíkových iontů MeSH
- magnetická rezonanční spektroskopie metody MeSH
- molekulární struktura MeSH
- nukleosidy chemická syntéza chemie MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- DNA sondy MeSH
- DNA-dependentní DNA-polymerasy MeSH
- fluor MeSH
- fluorescenční barviva MeSH
- nukleosidy MeSH
The rational design of 3d-metal-based single-molecule magnets (SMM) requires a fundamental understanding of their intrinsic electronic and structural properties and how they translate into experimentally observable features. Here, we determined the magnetic properties of the linear iron(I) silylamides K{crypt}[FeL2] and [KFeL2] (L = -N(Dipp)SiMe3; crypt = 4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo[8.8.8]hexacosan). For the former, slow-relaxation of the magnetization with a spin reversal barrier of Ueff = 152 cm-1 as well as a closed-waist magnetic hysteresis and magnetic blocking below 2.5 K are observed. For the more linear [KFeL2], in which the potassium cation is encapsulated by the aryl substituents of the amide ligands, the relaxation barrier and the blocking temperature increase to Ueff = 184 cm-1 and TB = 4.5 K, respectively. The increase is rationalized by a more pronounced axial anisotropy in [KFeL2] determined by dc-SQUID magnetometry. The effective relaxation barrier of [KFeL2] is in agreement with the energy spacing between the ground and first-excited magnetic states, as obtained by field-dependent IR-spectroscopy (178 cm-1), magnetic measurements (208 cm-1), as well as theoretical analysis (212 cm-1). In comparison with the literature, the results show that magnetic coercivity in linear iron(I) silylamides is driven by the degree of linearity in conjunction with steric encumbrance, whereas the ligand symmetry is a marginal factor.
- Publikační typ
- časopisecké články MeSH
Hydrides of actinides, their magnetic, electronic, transport, and thermodynamic properties are discussed within a general framework of H impact on bonding, characterized by volume expansion, affecting mainly the 5fstates, and a charge transfer towards H, which influences mostly the 6dand 7sstates. These general mechanisms have diverse impact on individual actinides, depending on the degree of localization of their 5fstates. Hydrogenation of uranium yields UH2and UH3, binary hydrides that are strongly magnetic due to the 5fband narrowing and reduction of the 5f-6dhybridization. Pu hydrides become magnetic as well, mainly as a result of the stabilization of the magnetic 5f5state and elimination of the admixture of the non-magnetic 5f6component.Ab-initiocomputational analyses, which for example suggest that the ferromagnetism ofβ-UH3is rather intricate involving two non-collinear sublattices, are corroborated by spectroscopic studies of sputter-deposited thin films, yielding a clean surface and offering a variability of compositions. It is found that valence-band photoelectron spectra cannot be compared directly with the 5fnground-state density of states. Being affected by electron correlations in the excited final states, they rather reflect the atomic 5fn-1multiplets. Similar tendencies can be identified also in hydrides of binary and ternary intermetallic compounds. H absorption can be used as a tool for fine tuning of electronic structure around a quantum critical point. A new direction is represented by actinide polyhydrides with a potential for high-temperature superconductivity.
- Klíčová slova
- actinides, hydrides, magnetism, phonons, spectroscopy,
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
In order to prepare a multifunctional magnetic material combining spin crossover together with single-molecular magnetism, co-crystallization of Fe(ii) and Co(ii) complexes of the pyridine derivative of cyclam (Py2-C = 1,8-bis(pyridin-2-ylmethyl)-1,4,8,11-tetraazacyclotetradecane) was performed. Complexes with the general formula [MII(Py2-C)](ClO4)2·H2O (MII = Fe (1), Co (2) or Fe0.4Co0.6 (3)) were prepared and thoroughly characterized. Based on X-ray molecular structures, they formed octahedral complexes with cis-arrangement of the coordinated pyridine moieties. Magnetic data revealed that the Fe(ii) complex 1 shows complete SCO with the transition temperature T1/2 = 141 K, which is preserved also in the mixed Fe/Co system 3 (T1/2 = 128 K). Co(ii) complex 2 behaves as a field-induced single-molecule magnet as well as the mixed system 3 with a direct and phonon bottleneck relaxation process, respectively. This is the first example of such Fe/Co solid solution providing SCO in combination with field-induced SMM properties. Unfortunately, the light-induced excited spin-state trapping (LIESST) effect was not observed either for the Fe(ii) complex 1 or the mixed system 3 and thus, the effect of SCO on SMM properties at low temperature could not be investigated in detail. Nevertheless, the obtained results clearly document the success of the solid solution methodology for the preparation of multifunctional magnetic materials.
- Publikační typ
- časopisecké články MeSH
Adiabatically swept pulses were originally designed for the purpose of broadband spin inversion. Later, unexpected advantages of their utilization were also found in other applications, such as refocusing to excite spin echoes, studies of chemical exchange or fragment-based drug design. Here, we present new experiments to characterize fast (ps-ns) protein dynamics, which benefit from little-known properties of adiabatic pulses. We developed a strategy for measuring cross-correlated cross-relaxation (CCCR) rates during adiabatic pulses. This experiment provides a linear combination of longitudinal and transverse CCCR rates, which is offset-independent across a typical amide (15)N spectrum. The pulse sequence can be recast to provide accurate transverse CCCR rates weighted by the populations of exchanging states. Sensitivity can be improved in systems in slow exchange. Finally, the experiments can be easily modified to yield residue-specific correlation times. The average correlation time of motions can be determined with a single experiment while at least two different experiments had to be recorded until now.
- Klíčová slova
- Adiabatic sweep, Cross-correlated cross relaxation, NMR, Protein dynamics,
- MeSH
- interakční proteinové domény a motivy MeSH
- lidé MeSH
- nukleární magnetická rezonance biomolekulární metody MeSH
- protein vázající CREB chemie MeSH
- ubikvitin chemie MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- CREBBP protein, human MeSH Prohlížeč
- protein vázající CREB MeSH
- ubikvitin MeSH
Magnetic layered materials have emerged recently as promising systems to introduce magnetism in structures based on two-dimensional (2D) materials and to investigate exotic magnetic ground states in the 2D limit. In this work, we apply high hydrostatic pressures up to P ≈ 8.7 GPa to the bulk layered antiferromagnet FePS3 to tune the collective lattice excitations (phonons) in resonance with magnetic excitations (magnons). Close to P = 4 GPa, the magnon-phonon resonance is achieved, and the strong coupling between these collective modes leads to the formation of new quasiparticles, the magnon-polarons, evidenced in our low-temperature Raman scattering experiments by a particular avoided crossing behavior between the phonon and the doubly degenerate antiferromagnetic magnon. At the pressure-induced magnon-phonon resonance, three distinct coupled modes emerge. As it is mainly defined by intralayer properties, we show that the energy of the magnon is nearly pressure-independent. We additionally apply high magnetic fields up to B = 30 T to fully identify and characterize the magnon excitations and to explore the different magnon-polaron regimes for which the phonon has an energy lower than, equal to, or higher than the magnon energy. The description of our experimental data requires introducing a phonon-phonon coupling not taken into account in actual calculations.
- Klíčová slova
- Raman scattering, extreme conditions, magnetic materials, optical spectroscopy, van der Waals materials,
- Publikační typ
- časopisecké články MeSH
