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- ItemTuning the spin coherence time of Cu(II)−(bis)oxamato and Cu(II)−(bis)oxamidato complexes by advanced ESR pulse protocols(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2017-4-27) Zaripov, Ruslan; Vavilova, Evgeniya; Khairuzhdinov, Iskander; Salikhov, Kev; Voronkova, Violeta; Abdulmalic, Mohammad A.; Meva, Francois E.; Weheabby, Saddam; Rüffer, Tobias; Büchner, Bernd; Kataev, VladislavWe have investigated with the pulsed ESR technique at X- and Q-band frequencies the coherence and relaxation of Cu spins S = 1/2 in single crystals of diamagnetically diluted mononuclear [n-Bu4N]2[Cu(opba)] (1%) in the host lattice of [n-Bu4N]2[Ni(opba)] (99%, opba = o-phenylenebis(oxamato)) and of diamagnetically diluted mononuclear [n-Bu4N]2[Cu(opbon-Pr2)] (1%) in the host lattice of [n-Bu4N]2[Ni(opbon-Pr2)] (99%, opbon-Pr2 = o-phenylenebis(N(propyl)oxamidato)). For that we have measured the electron spin dephasing time Tm at different temperatures with the two-pulse primary echo and with the special Carr–Purcell–Meiboom–Gill (CPMG) multiple microwave pulse sequence. Application of the CPMG protocol has led to a substantial increase of the spin coherence lifetime in both complexes as compared to the primary echo results. It shows the efficiency of the suppression of the electron spin decoherence channel in the studied complexes arising due to spectral diffusion induced by a random modulation of the hyperfine interaction with the nuclear spins. We argue that this method can be used as a test for the relevance of the spectral diffusion for the electron spin decoherence. Our results have revealed a prominent role of the opba4– and opbon-Pr24– ligands for the dephasing of the Cu spins. The presence of additional 14N nuclei and protons in [Cu(opbon-Pr2)]2– as compared to [Cu(opba)]2– yields significantly shorter Tm times. Such a detrimental effect of the opbon-Pr24− ligands has to be considered when discussing a potential application of the Cu(II)−(bis)oxamato and Cu(II)−(bis)oxamidato complexes as building blocks of more complex molecular structures in prototype spintronic devices. Furthermore, in our work we propose an improved CPMG pulse protocol that enables elimination of unwanted echoes that inevitably appear in the case of inhomogeneously broadened ESR spectra due to the selective excitation of electron spins.
- ItemProbing the magnetic superexchange couplings between terminal CuII ions in heterotrinuclear bis(oxamidato) type complexes(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2017-4-6) Abdulmalic, Mohammad A.; Weheabby, Saddam; Meva, Francois E.; Aliabadi, Azar; Kataev, Vladislav; Büchner, Bernd; Schleife, Frederik; Kersting, Berthold; Rüffer, TobiasThe reaction of one equivalent of [n-Bu4N]2[Ni(opboR2)] with two equivalents of [Cu(pmdta)(X)2] afforded the heterotrinuclear CuIINiIICuII containing bis(oxamidato) type complexes [Cu2Ni(opboR2)(pmdta)2]X2 (R = Me, X = NO3– (1); R = Et, X = ClO4– (2); R = n-Pr, X = NO3– (3); opboR2 = o-phenylenebis(NR-substituted oxamidato); pmdta = N,N,N’,N”,N”-pentamethyldiethylenetriamine). The identities of the heterotrinuclear complexes 1–3 were established by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction studies, which revealed the cationic complex fragments [Cu2Ni(opboR2)(pmdta)2]2+ as not involved in any further intermolecular interactions. As a consequence thereof, the complexes 1–3 possess terminal paramagnetic [Cu(pmdta)]2+ fragments separated by [NiII(opboR2)]2– bridging units representing diamagnetic SNi = 0 states. The magnetic field dependence of the magnetization M(H) of 1–3 at T = 1.8 K has been determined and is shown to be highly reproducible with the Brillouin function for an ideal paramagnetic spin = 1/2 system, verifying experimentally that no magnetic superexchange couplings exists between the terminal paramagnetic [Cu(pmdta)]2+ fragments. Susceptibility measurements versus temperature of 1–3 between 1.8–300 K were performed to reinforce the statement of the absence of magnetic superexchange couplings in these three heterotrinuclear complexes.
- ItemMagnetic superexchange interactions: Trinuclear bis(oxamidato) versus bis(oxamato) type complexes(Cambridge : Royal Society of Chemistry, 2015) Abdulmalic, Mohammad A.; Aliabadi, Azar; Petr, Andreas; Krupskaya, Yulia; Kataev, Vladislav; Büchner, Bernd; Zaripov, Ruslan; Vavilova, Evgeniya; Voronkova, Violeta; Salikov, Kev; Hahn, Torsten; Kortus, Jens; Meva, Francois Eya’ane; Schaarschmidt, Dieter; Rüffer, TobiasThe diethyl ester of o-phenylenebis(oxamic acid) (opbaH2Et2) was treated with an excess of RNH2 in MeOH to cause the exclusive formation of the respective o-phenylenebis(N(R)-oxamides) (opboH4R2, R = Me 1, Et 2, nPr 3) in good yields. Treatment of 1–3 with half an equivalent of [Cu2(AcO)4(H2O)2] or one equivalent of [Ni(AcO)2(H2O)4] followed by the addition of four equivalents of [nBu4N]OH resulted in the formation of mononuclear bis(oxamidato) type complexes [nBu4N]2[M(opboR2)] (M = Ni, R = Me 4, Et 5, nPr 6; M = Cu, R = Me 7, Et 8, nPr 9). By addition of two equivalents of [Cu(pmdta)(NO3)2] to MeCN solutions of 7–9, novel trinuclear complexes [Cu3(opboR2)(L)2](NO3)2 (L = pmdta, R = Me 10, Et 11, nPr 12) could be obtained. Compounds 4–12 have been characterized by elemental analysis and NMR/IR spectroscopy. Furthermore, the solid state structures of 4–10 and 12 have been determined by single-crystal X-ray diffraction studies. By controlled cocrystallization, diamagnetically diluted 8 and 9 (1%) in the host lattice of 5 and 6 (99%) (8@5 and 9@6), respectively, in the form of single crystals have been made available, allowing single crystal ESR studies to extract all components of the g-factor and the tensors of onsite CuA and transferred NA hyperfine (HF) interaction. From these studies, the spin density distribution of the [Cu(opboEt2)]2− and [Cu(opbonPr2)]2− complex fragments of 8 and 9, respectively, could be determined. Additionally, as a single crystal ENDOR measurement of 8@5 revealed the individual HF tensors of the N donor atoms to be unequal, individual estimates of the spin densities on each N donor atom were made. The magnetic properties of 10–12 were studied by susceptibility measurements versus temperature to give J values varying from −96 cm−1 (10) over −104 cm−1 (11) to −132 cm−1 (12). These three trinuclear CuII-containing bis(oxamidato) type complexes exhibit J values which are comparable to and slightly larger in magnitude than those of related bis(oxamato) type complexes. In a summarizing discussion involving experimentally obtained ESR results (spin density distribution) of 8 and 9, the geometries of the terminal [Cu(pmdta)]2+ fragments of 12 determined by crystallographic studies, together with accompanying quantum chemical calculations, an approach is derived to explain these phenomena and to conclude if the spin density distribution of mononuclear bis(oxamato)/bis(oxamidato) type complexes could be a measure of the J couplings of corresponding trinuclear complexes.
- ItemOrbital reconstruction in nonpolar tetravalent transition-metal oxide layers(London : Nature Publishing Group, 2015) Bogdanov, Nikolay A.; Katukuri, Vamshi M.; Romhányi, Judit; Yushankhai, Viktor; Kataev, Vladislav; Büchner, Bernd; van den Brink, Jeroen; Hozoi, LiviuA promising route to tailoring the electronic properties of quantum materials and devices rests on the idea of orbital engineering in multilayered oxide heterostructures. Here we show that the interplay of interlayer charge imbalance and ligand distortions provides a knob for tuning the sequence of electronic levels even in intrinsically stacked oxides. We resolve in this regard the d-level structure of layered Sr2IrO4 by electron spin resonance. While canonical ligand-field theory predicts g
- ItemInsights into the Spin–Orbital Entanglement in Complex Iridium Oxides from High-Field ESR Spectroscopy(Wien [u.a.] : Springer, 2021) Kataev, VladislavComplex iridium oxides have attracted recently a substantial interdisciplinary attention due to an intimate entanglement of spin and orbital degrees of freedom which may give rise to a novel spin–orbital Mott insulating behavior and exotic quantum spin liquid phases. Electron spin resonance (ESR) spectroscopy is known to be an instructive tool for studying the spin–orbital coupling (SOC) effects as it can directly access the relevant parameters sensitive to SOC, such as the g factor tensor, magnetic anisotropy gaps and spin dynamics. In this article, a systematic study at the Leibniz IFW Dresden of the static and dynamic properties of selected Ir-based materials with multi-frequency high-field ESR spectroscopy will be reviewed. Specifically, evidence for a surprisingly isotropic antiferromagnetic spin dynamics and the inversion of the orbital states in the prototypical spin–orbital Mott insulator Sr 2IrO 4, observation of the collective resonance modes in the family of double perovskites La 2BIrO 6 (B = Cu, Co) and the origin of the unexpected magnetism in the double perovskite Ba 2YIrO 6 will be highlighted. © 2021, The Author(s).
- ItemRolled‐Up Self‐Assembly of Compact Magnetic Inductors, Transformers, and Resonators(Weinheim : Wiley-VCH Verlag GmbH & Co. KG, 2018-8-17) Karnaushenko, Dmitriy D.; Karnaushenko, Daniil; Grafe, Hans‐Joachim; Kataev, Vladislav; Büchner, Bernd; Schmidt, Oliver G.3D self-assembly of lithographically patterned ultrathin films opens a path to manufacture microelectronic architectures with functionalities and integration schemes not accessible by conventional 2D technologies. Among other microelectronic components, inductances, transformers, antennas, and resonators often rely on 3D configurations and interactions with electromagnetic fields requiring exponential fabrication efforts when downscaled to the micrometer range. Here, the controlled self-assembly of functional structures is demonstrated. By rolling up ultrathin films into cylindrically shaped microelectronic devices, electromagnetic resonators, inductive and mutually coupled coils are realized. Electrical performance of these devices is improved purely by transformation of a planar into a cylindrical geometry. This is accompanied by an overall downscaling of the device footprint area by more than 50 times. Application of compact self-assembled microstructures has significant impact on electronics, reducing size, fabrication efforts, and offering a wealth of new features in devices by 3D shaping.
- ItemPhononic-magnetic dichotomy of the thermal Hall effect in the Kitaev material Na2 Co2 TeO6(College Park, MD : APS, 2023) Gillig, Matthias; Hong, Xiaochen; Wellm, Christoph; Kataev, Vladislav; Yao, Weiliang; Li, Yuan; Büchner, Bernd; Hess, ChristianThe quest for a half-quantized thermal Hall effect of a Kitaev system represents an important tool to probe topological edge currents of emergent Majorana fermions. Pertinent experimental findings for α-RuCl3 are, however, strongly debated, and it has been argued that the thermal Hall signal stems from phonons or magnons rather than from Majorana fermions. Here, we investigate the thermal Hall effect of the Kitaev candidate material Na2Co2TeO6, and we show that the measured signal emerges from at least two components, phonons and magnetic excitations. This dichotomy results from our discovery that the longitudinal and transversal heat conductivities share clear phononic signatures, while the transversal signal changes sign upon entering the low-temperature, magnetically ordered phase. Our results demonstrate that uncovering a genuinely quantized magnetic thermal Hall effect in Kitaev topological quantum spin liquids such as α-RuCl3 and Na2Co2TeO6 requires disentangling phonon vs magnetic contributions, including potentially fractionalized excitations such as the expected Majorana fermions.
- ItemLong-range magnetic order in the ~S=1/2 triangular lattice antiferromagnet KCeS2(Amsterdam : SciPost Foundation, 2020) Bastien, Gaël; Rubrecht, Bastian; Haeussler, Ellen; Schlender, Philipp; Zangeneh, Ziba; Avdoshenko, Stanislav; Sarkar, Rajib; Alfonsov, Alexey; Luther, Sven; Onykiienko, Yevhen A.; Walker, Helen C.; Kühne, Hannes; Grinenko, Vadim; Guguchia, Zurab; Kataev, Vladislav; Klauss, Hans-Henning; Hozoi, Liviu; van den Brink, Jeroen; Inosov, Dmytro S.; Büchner, Bernd; Wolter, Anja U.B.; Doert, ThomasRecently, several putative quantum spin liquid (QSL) states were discovered in ~S=1/2 rare-earth based triangular-lattice antiferromagnets (TLAF) with the delafossite structure. A way to clarify the origin of the QSL state in these systems is to identify ways to tune them from the putative QSL state towards long-range magnetic order. Here, we introduce the Ce-based TLAF KCeS2 and show via low-temperature specific heat and μSR investigations that it yields magnetic order below TN=0.38 K despite the same delafossite structure. We identify a well separated ~S=1/2 ground state for KCeS2 from inelastic neutron scattering and embedded-cluster quantum chemical calculations. Magnetization and electron spin resonance measurements on single crystals indicate a strong easy-plane g~factor anisotropy, in agreement with the ab initio calculations. Finally, our specific-heat studies reveal an in-plane anisotropy of the magnetic field-temperature phase diagram which may indicate anisotropic magnetic interactions in KCeS2.