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- ItemPlasma-assisted synthesis and high-resolution characterization of anisotropic elemental and bimetallic core-shell magnetic nanoparticles(Frankfurt, M. : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2014) Hennes, M.; Lotnyk, A.; Mayr, S.G.Magnetically anisotropic as well as magnetic core-shell nanoparticles (CS-NPs) with controllable properties are highly desirable in a broad range of applications. With this background, a setup for the synthesis of heterostructured magnetic core-shell nanoparticles, which relies on (optionally pulsed) DC plasma gas condensation has been developed. We demonstrate the synthesis of elemental nickel nanoparticles with highly tunable sizes and shapes and Ni@Cu CS-NPs with an average shell thickness of 10 nm as determined with scanning electron microscopy, high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy measurements. An analytical model that relies on classical kinetic gas theory is used to describe the deposition of Cu shell atoms on top of existing Ni cores. Its predictive power and possible implications for the growth of heterostructured NP in gas condensation processes are discussed.
- ItemDinuclear lanthanide complexes supported by a hybrid salicylaldiminato/calix[4]arene-ligand: Synthesis, structure, and magnetic and luminescence properties of (HNEt3)[Ln2(HL)(L)] (Ln = SmIII, EuIII, GdIII, TbIII)(London : Soc., 2019) Ullmann, Steve; Hahn, Peter; Blömer, Laura; Mehnert, Anne; Laube, Christian; Abel, Bernd; Kersting, BertholdThe synthesis, structures, and properties of a new calix[4]arene ligand with an appended salicylaldimine unit (H4L = 25-[2-((2-methylphenol)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) and four lanthanide complexes (HNEt3)[Ln2(HL)(L)] (Ln = SmIII (4), EuIII (5), GdIII (6), and TbIII (7)) are reported. X-ray crystallographic analysis (for 4 and 6) reveals an isostructural series of dimeric complexes with a triply-bridged NO3Ln(μ-O)2(OH⋯O)LnO3N core and two seven coordinated lanthanide ions. According to UV-vis spectrometric titrations in MeCN and ESI-MS the dimeric nature is maintained in solution. The apparent stability constants range between logK = 5.8 and 6.3. The appended salicylaldimines sensitize EuIII and TbIII emission (λexc 311 nm) in the solid state or immersed in a polycarbonate glass at 77 K (for 5, 7) and at 295 K (for 7). © The Royal Society of Chemistry 2019.
- ItemMixed-ligand lanthanide complexes supported by ditopic bis(imino-methyl)-phenol/calix[4]arene macrocycles: synthesis, structures, and luminescence properties of [Ln2(L2)(MeOH)2] (Ln = La, Eu, Tb, Yb)(London : Soc., 2020) Ullmann, Steve; Hahn, Peter; Mini, Parvathy; Tuck, Kellie L.; Kahnt, Axel; Abel, Bernd; Gutierrez Suburu, Matias E.; Strassert, Cristian A.; Kersting, BertholdThe lanthanide binding ability of a macrocyclic ligand H6L2 comprising two bis(iminomethyl)phenol and two calix[4]arene units has been studied. H6L2 is a ditopic ligand which provides dinuclear neutral complexes of composition [Ln2(L2)(MeOH)2] (Ln = La (1), Eu (2), Tb (3), and Yb (4)) in very good yield. X-ray crystal structure analyses for 2 and 3 show that (L2)6- accommodates two seven coordinated lanthanide ions in a distorted monocapped trigonal prismatic/octahedral coordination environment. UV-vis spectroscopic titrations performed with La3+, Eu3+, Tb3+ and Yb3+ ions in mixed MeOH/CH2Cl2 solution (I = 0.01 M NBu4PF6) reveal that a 2 : 1 (metal : ligand) stoichiometry is present in solution, with log K11 and K21 values ranging from 5.25 to 6.64. The ratio α = K11/K21 of the stepwise formation constants for the mononuclear (L2 + M = ML2, log K11) and the dinuclear complexes (ML2 + M = M2L2, log K21) was found to be invariably smaller than unity indicating that the binding of the first Ln3+ ion augments the binding of the second Ln3+ ion. The present complexes are less luminescent than other seven-coordinated Eu and Tb complexes, which can be traced to vibrational relaxation of excited EuIII and TbIII states by the coligated MeOH and H2O molecules and/or low-lying ligand-to-metal charge-transfer (LMCT) states. © 2020 The Royal Society of Chemistry.
- ItemPolymeric monolithic materials: Syntheses, properties, functionalization and applications(Amsterdam : Elsevier, 2007) Buchmeiser, M.R.The synthetic particularities for the synthesis of polymer-based monolithic materials are summarized. In this context, monoliths prepared via thermal-, UV- or electron-beam triggered free radical polymerization, controlled TEMPO-mediated radical polymerization, polyaddition, polycondensation as well as living ring-opening metathesis polymerization (ROMP) will be covered. Particular attention is devoted to the aspects of controlling pore sizes, pore volumes and pore size distributions as well as functionalization of these supports. Finally, selected, recent applications in separation science, (bio-) catalysis and chip technology will be summarized. © 2007 Elsevier Ltd. All rights reserved.