EPR and Electronic Spectra of (3-chloroanilinium)8[CuCl6]Cl4: Evidence for Tetragonally Elongated CuCl64- Ions with the Long Axis Disordered in 2-Dimensions

Stratemeier, Horst; Wagner, Burghard; Krausz, Elmars; Linder, Rolf; Schmidtke, Hans‐Herbert; Pebler, J.; Hatfield, William E.; Haar, Leo ter; Reinen, D.; Hitchman, Michael A.

doi:10.1021/ic00089a004

Cited by 34 publications

(40 citation statements)

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“…91,[94][95][96][97][98][99][100][101][102][103][104] All three 133 Cs NMR peaks shift to higher frequency as the temperature is increased (Figures 5a and 5b, and Table S6), but each has a distinct temperature dependence. [74][75][76]80,81 Peak-1 changes slowly with temperature; the small temperature dependence (0.08 ppm/K) for this peak is 5c). The fact that the temperature dependence is Curie-like (i.e., the paramagnetic effect decreases with increasing temperature) and additive indicates that either contact occurs through two uncoupled copper centers or that the coupling between the two copper centers is smaller than the thermal energy (which is consistent with observations reported previously).…”

Section: Resultsmentioning

confidence: 90%

“…The elemental analysis of these materials using EDX spectroscopy (Table S1) indicating the presence of exchange-coupled copper pairs. 75 This intriguing observation suggests that copper-copper pairs form with a higher-than statistical probability. Exchange coupling is expected to emerge because of the interaction of the electrons on one copper center with electrons on another copper center, through the orbitals of intervening non-magnetic atoms between them.…”

Section: Resultsmentioning

confidence: 99%

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Cu(II)-Doped Cs₂SbAgCl₆ Double Perovskite: A Lead-Free, Low-Bandgap Material

et al. 2018

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Lead-free halide double perovskites with a generic formula of A2B'(III)B"(I)X6 (A and B are cations and X is a halide anion) are being explored as a less toxic, higher thermal-and moisturestable alternatives to well-studied lead halide perovskite (APbX3) solar energy absorbers. However, the absorption profiles of most of the double perovskites reported to date have larger bandgaps (> 2 eV) that are poorly aligned with the solar spectrum, reducing their photoconversion efficiency. Here, we present new heterovalent paramagnetic Cu 2+-doped Cs2SbAgCl6 double perovskites that exhibit dramatic shifts in their bandgaps from ~ 2.6 eV (Cs2SbAgCl6, parent) to ~1 eV (Cu 2+-doped Cs2SbAgCl6). Powder X-ray diffraction patterns of the Cu 2+-doped polycrystalline materials indicate long-range crystallinity with non-uniform microstrain in the crystal lattice. To decode the dopant, complementary magnetic resonance spectroscopy techniques, solid-state nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR), unravel the complex short-and medium-range structure of these novel double perovskite materials. Variable temperature 133 Cs NMR spectroscopy reveals that paramagnetic Cu 2+ ions are incorporated within the double perovskite material impacting the 133 Cs NMR through a Fermi contact interaction. Finally, a comprehensive stress test of the material's long-term (up to 365 days) thermal and moisture stability indicate excellent resistance to environmental exposure.

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Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Cu(II)-Doped Cs₂SbAgCl₆ Double Perovskite: A Lead-Free, Low-Bandgap Material

et al. 2018

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“…The octahedral Cu(II) units in the crystals of K 2 CuF 4 , Ba 2 CuF 6 , and so forth, were originally misinterpreted as compressed by EPR measurements and X‐ray data. More elaborate investigations, including Extended X‐Ray Absorption Fine Structure (EXAFS) measurements, showed that, in fact, the local octahedra are elongated 79–81. The evaluated E JT values are in the range 2400–3400 cm −1 for all used functionals, with the exception of OPBE, which gives a very high JT stabilization energy.…”

Section: Resultsmentioning

confidence: 94%

The role of macrophage inhibitory factor in tumorigenesis and central nervous system tumors

Bach

Deuster

Balzer‐Geldsetzer

et al. 2009

Cancer

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Poly(trimethoxy silylpropylaniline), a nanoporous (pore diameter of 2.4 nm), electroactive (stable reversible redox characteristics), electrochromic (yellow at −0.10 V, blue green at +0.50 V, and dark green at +0.70 V), and pH‐sensitive, silica–polyaniline (PANI) hybrid material (designated as KGM‐1) has been synthesized in powder form by a simple one‐pot chemical synthesis as well as a “thin nanolayered film” by cyclic voltammetry. High‐resolution transmission image of KGM‐1 informs that the particles are spherical, with diameters in the range of 0.5–1.5 μm. X‐ray diffraction pattern of pristine KGM‐1 confirms the combined presence of ordered silica network and PANI chains. The surface area of calcined KGM‐1 is 40 m2/g (∼15 times higher than KGM‐1), and the average pore size is 2.4 nm. The N2 adsorption features also inform that PANI is present as a uniform layer within the pores of silica and because of that the silica pores are not completely blocked. The reversible redox transitions in PANI units and nanoporosity of KGM‐1 are effectively used for the electro‐driven loading/release of DNA or adenosine 5′‐triphosphate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

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“…This impression is reinforced by its powder EPR spectrum, which shows a pattern of g-values (g > = 2.20, g || = 2.04). 23 At first glance, that is consistent with an unpaired electron in a d z 2 orbital on the copper ion, which would lead to g > > g || = 2.0023, 24 and again implies a Jahn-Teller compressed structure (Scheme 1). However, the EPR g || value (2.04) is higher than would be expected for a {d z 2} 1 configuration (2.00).…”

Section: Dynamic and Disordered Jahn-teller Distortionsmentioning

confidence: 88%

“…That maps perfectly onto the g-pattern expected for a Jahn-Tellerelongated, {d x 2 Ày 2} 1 copper(II) centre (g 1 > g 2 Z g 3 > 2.0023 24 ), while the true g 1 and g 2 values agree well with the averaged g > value (2.20) from the initial study. 23 A survey of copper(II) complexes that are known to show Jahn-Teller disorder is given in the ESI. † Most of these involve polyatomic organic ligands, which complicates the interpretation of the crystal structures.…”

Section: Dynamic and Disordered Jahn-teller Distortionsmentioning

confidence: 99%

Jahn–Teller distortions in transition metal compounds, and their importance in functional molecular and inorganic materials

2013

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5This tutorial review discusses the structural and electronic consequences of the Jahn-Teller effect in transition metal complexes, focussing on copper(II) compounds which tend to be the most studied. The nature of a Jahn-Teller distortion in molecular complexes and extended lattices can be manipulated by application of pressure or temperature, by doping a molecule into a host lattice, or simply by molecular design. Many of these results have been achieved using compounds with a trans-[CuX 4 Y 2 ] coordination 10 sphere, which seems to afford copper centres that are particularly sensitive to their environment. JahnTeller distortions lead to some unusual phenomena in molecular magnetism, and are important to the functionality of important classes of conducting and superconducting ceramics.

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EPR and Electronic Spectra of (3-chloroanilinium)8[CuCl6]Cl4: Evidence for Tetragonally Elongated CuCl64- Ions with the Long Axis Disordered in 2-Dimensions

Cited by 34 publications

References 1 publication

Cu(II)-Doped Cs₂SbAgCl₆ Double Perovskite: A Lead-Free, Low-Bandgap Material

Cu(II)-Doped Cs₂SbAgCl₆ Double Perovskite: A Lead-Free, Low-Bandgap Material

The role of macrophage inhibitory factor in tumorigenesis and central nervous system tumors

Jahn–Teller distortions in transition metal compounds, and their importance in functional molecular and inorganic materials

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EPR and Electronic Spectra of (3-chloroanilinium)8[CuCl6]Cl4: Evidence for Tetragonally Elongated CuCl64- Ions with the Long Axis Disordered in 2-Dimensions

Cited by 34 publications

References 1 publication

Cu(II)-Doped Cs2SbAgCl6 Double Perovskite: A Lead-Free, Low-Bandgap Material

Cu(II)-Doped Cs2SbAgCl6 Double Perovskite: A Lead-Free, Low-Bandgap Material

The role of macrophage inhibitory factor in tumorigenesis and central nervous system tumors

Jahn–Teller distortions in transition metal compounds, and their importance in functional molecular and inorganic materials

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Product

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Cu(II)-Doped Cs₂SbAgCl₆ Double Perovskite: A Lead-Free, Low-Bandgap Material

Cu(II)-Doped Cs₂SbAgCl₆ Double Perovskite: A Lead-Free, Low-Bandgap Material