The synthesis and characterization is reported of (C NH ) SnBr , a novel organic metal halide hybrid with a zero-dimensional (0D) structure, in which individual seesaw-shaped tin (II) bromide anions (SnBr ) are co-crystallized with 1-butyl-1-methylpyrrolidinium cations (C NH ). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep-red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. The unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals to exhibit the intrinsic properties of individual SnBr species, and 2) the seesaw structure enabling a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.
Organic metal halide hybrids with zero-dimensional (0D) structure at the molecular level, or single-crystalline bulk assemblies of metal halides, are an emerging class of light-emitting materials with high photoluminescence quantum efficiencies (PLQEs) and color tunability. Here we report the synthesis and characterization of a new single-crystalline bulk assembly of metal halide clusters, (bmpy) 9 [ZnCl 4 ] 2 [Pb 3 Cl 11 ] (bmpy: 1-butyl-1-methylpyrrolidinium), which exhibits green emission peaked at 512 nm with a remarkable near-unity PLQE at room temperature. Detailed structural and photophysical studies suggest that there are two emitting states in [Pb 3 Cl 11 ] 5− clusters, whose populations are strongly dependent on the surrounding molecular environment that controls the excitedstate structural distortion of [Pb 3 Cl 11 ] 5− clusters. High chemical-and photostability have also been demonstrated in this new material.
Reactions of Fe(II) precursors with the tetradentate ligand S,S'-bis(2-pyridylmethyl)-1,2-thioethane (bpte) and monodentate NCE(-) coligands afforded mononuclear complexes [Fe(bpte)(NCE)2] (1, E = S; 2, E = Se; 3, E = BH3) that exhibit temperature-induced spin crossover (SCO). As the ligand field strength increases from NCS(-) to NCSe(-) to NCBH3(-), the SCO shifts to higher temperatures. Complex 1 exhibits only a partial (15%) conversion from the high-spin (HS) to the low-spin (LS) state, with an onset around 100 K. Complex 3 exhibits a complete SCO with T1/2 = 243 K. While the γ-2 polymorph also shows the complete SCO with T1/2 = 192 K, the α-2 polymorph exhibits a two-step SCO with the first step leading to a 50% HS → LS conversion with T1/2 = 120 K and the second step proceeding incompletely in the 80-50 K range. The amount of residual HS fraction of α-2 that remains below 60 K depends on the cooling rate. Fast flash-cooling allows trapping of as much as 45% of the HS fraction, while slow cooling leads to a 14% residual HS fraction. The slowly cooled sample of α-2 was subjected to irradiation in the magnetometer cavity resulting in a light-induced excited spin state trapping (LIESST) effect. As demonstrated by Mössbauer spectroscopy, an HS fraction of up to 85% could be achieved by irradiation at 4.2 K.
The synthesis and characterization is reported of (C 9 NH 20 ) 2 SnBr 4 ,anovel organic metal halide hybrid with azero-dimensional (0D) structure,inwhichindividual seesawshaped tin (II) bromide anions (SnBr 4 2À )a re co-crystallized with 1-butyl-1-methylpyrrolidinium cations (C 9 NH 20
The synthesis and structural characterization is reported for [Fe(dien)2][FeSe2]2 and [Fe(tren)][FeSe2]2, two new mixed-valence compounds that contain infinite ∞(1)(FeSe2) tetrahedral chains separated by Fe-amine complexes. The inter- and intra-chain magnetic interactions can be controlled by changing the denticity of the amine while preserving the general structural motif.
Fragments of the superconducting FeSe layer, FeSe2 tetrahedral chains, were stabilized in the crystal structure of a new mixed-valent compound Fe3Se4(en)2 (en = ethylenediamine) synthesized from elemental Fe and Se. The FeSe2 chains are separated from each other by means of Fe(en)2 linkers. Mössbauer spectroscopy and magnetometry reveal strong magnetic interactions within the FeSe2 chains which result in antiferromagnetic ordering below 170 K. According to DFT calculations, anisotropic transport and magnetic properties are expected for Fe3Se4(en)2. This compound offers a unique way to manipulate the properties of the Fe-Se infinite fragments by varying the topology and charge of the Fe-amino linkers.
We report two solvothermal pathways toward intercalated iron sulfide, [Fe 8 S 10 ]Fe(en) 3 •en 0.5 (en = ethylenediamine), featuring [Fe 8 S 10 ] 2− layers stacked by [Fe(en) 3 ] 2+ cations and free ethylenediamine molecules. [Fe 8 S 10 ]Fe(en) 3 •en 0.5 is synthesized in a simple single-step method from Fe and S in ethylenediamine with addition of NH 4 Cl mineralizer as well as from solvothermal treatment of mackinawite, tetragonal FeS. In situ synchrotron powder X-ray diffraction experiments reveal a clear transformation of tetragonal FeS into [Fe 8 S 10 ]Fe(en) 3 •en 0.5 upon reaction with ethylenediamine. In-house control synthetic experiments confirmed the chemical process, whereby ethylenediamine leaches iron solely from the tetragonal Fe−S layers to form [Fe(en) 3 ] 2+ complexes and thereby oxidize the intralayer iron to Fe 2.25+ . Our report emphasizes that, in layered iron chalcogenides, diamines can intercalate as charged coordination complexes in tandem with neutral diamine molecules.
The nitroxyl radical 1-methyl-2-azaadamantane N-oxyl (Me-AZADO) exhibits magnetic bistability arising
from a radical/dimer
interconversion. The transition from the rotationally disordered paramagnetic
plastic crystal, Me-AZADO, to the ordered diamagnetic crystalline
phase, (Me-AZADO)2, has been conclusively demonstrated
by crystal structure determination from high-resolution powder diffraction
data and by solid-state NMR spectroscopy. The phase change is characterized
by a wide thermal hysteresis with high sensitivity to even small applied
pressures. The molecular dynamics of the phase transition from the
plastic crystal to the conventional crystalline phase has been tracked
by solid-state (1H and 13C) NMR and EPR spectroscopies.
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