Symmetry‐Breaking Transitions in SmCu1+δAs2—χPχ(δ = 0 — 0.2, χ = 0 — 2). Effect of P and Additional Cu Atoms on Crystal Structures and Magnetic Properties

Crystal structures of the compounds SmCu_1+δAs_2—χP_χ (δ = 0 — 0.2, χ = 0 — 2) undergoing symmetry‐breaking transitions and SmCuP_2.3 have been investigated by the X‐ray single crystal and powder methods. While the phases SmCuAs₂ through SmCuAs_1.22P_0.78 retain the tetragonal HfCuSi₂ structure (P4/nmm space group), the compounds SmCuAs_1.11P_0.89 through SmCuAs_0.56P_1.44 adopt the GdCuAs_1.15P_0.85—type structure (Pmmn space group), an orthorhombic variant of the HfCuSi₂‐type. Further distortion follows in SmCuAs_0.33P_1.67 through SmCuP_2.3, the powder patterns of which were indexed in the P2/n space group (P2/c in a standard setting). According to Landau theory the transitions from tetragonal SmCuAs_1.22P_0.78 to orthorhombic SmCuAs_1.11P_0.89 and from orthorhombic SmCuAs_0.56P_1.44 to monoclinic SmCuAs_0.33P_1.67 can be continuous. Introducing extra copper into some of the orthorhombic arsenophosphides restabilizes tetragonal phases (0 < δ ≤ 0.2) with the P4/nmm symmetry, and the reverse transition Pmmn → P4/nmmcan be continuous. Inserting copper atoms into monoclinic SmCuP₂ yields the SmCu_1+δP₂ phosphides with Cmmm symmetry, and this transition is first‐order. Single crystals of SmCu_1.05As_1.67P_0.33, SmCu_1.07As_0.85P_1.15 and SmCu_1.15P₂ have been prepared using iodine as a mineralizing agent. Their structures have partially occupied Cu sites around the square As/P or P layers and they are a stuffed variant of the HfCuSi₂ structure for SmCu_1.05As_1.67P_0.33 (P4/nmm, a = 3.9163(6), c = 9.932(2)Å), a stuffed GdCuAs_1.15P_0.85 structure for SmCu_1.07As_0.85P_1.15 (Pmmn, a = 3.859(1), b = 3.862(1), c = 9.852(3)Å) and a CeCu_1.12P_1.97‐type structure for SmCu_1.15P₂ (Cmmm, a = 5.453(3), b = 19.511(10), c = 5.439(3)Å). The P net in SmCu_1.15P₂ is broken into rectangular units. The results of magnetic measurements for SmCuAsP are reported.     

Ionization of aniline and its N-methyl and N-phenyl substituted derivatives by (free) electron transfer to n-butyl chloride parent radical cations

The electron transfer from aniline and its N-methyl as well as N-phenyl substituted derivatives (N-methylaniline, N,N-dimethylaniline, diphenylamine, triphenylamine) to parent solvent radical cations was studied by electron pulse radiolysis in n-butyl chloride solution. The ionization results in the case of aniline (ArNH2) and the secondary aromatic amines (Ar2NH, Ar(Me)NH) in the synchronous and direct formation of amine radical cations, as well as aminyl radicals, in comparable amounts. Subsequently, ArNH2*+ deprotonates in a delayed reaction with the present nucleophile Cl-, and forms further ArNH*. In contrast, tertiary aromatic amines such as triphenylamine and dimethylaniline yield primarily the corresponding amine radical cations Ar3N*+ or Ar(Me2)N*+, only. The persistent Ar3N*+ forms a charge transfer complex (dimer) with the parent amine molecule, whereas Ar(Me2)N*+ deprotonates to carbon-centered radicals Ar(Me)NCH2*.     

EPR studies of amine radical cations. Part 2. Thermal and photo-induced rearrangements of propargylamine and allylamine radical cations in low-temperature freon matrices

Matrix EPR studies and quantum chemical calculations have been used to characterize the consecutive H-atom shifts undergone by the nitrogen-centered parent radical cations of propargylamine (1b*+) and allylamine (5*+) on thermal or photoinduced activation. The radical cation rearrangements of these unsaturated parent amines occur initially by a 1,2 H-atom shift from C1 to C2 with pi-bond formation at the positively charged nitrogen; this is followed by a consecutive reaction involving a second H-atom shift from C2 to C3. Thus, exposure to red light (lambda > 650 nm) converts 1b*+ to the vinyl-type distonic radical cation 2*+ which in turn is transformed on further photolysis with blue-green light (lambda approximately 400-600 nm) to the allene-type heteroallylic radical cation 3*+. Calculations show that the energy ordering is 1b*+ > 2*+ > 3*+, so that the consecutive H-atom shifts are driven by the formation of more stable isomers. Similarly, the parent radical cation of allylamine 5*+ undergoes a spontaneous 1,2-hydrogen atom shift from C1 to C2 at 77 K with a t1/2 of approximately 1 h to yield the distonic alkyl-type iminopropyl radical cation 6*+; this thermal reaction is attributed largely to quantum tunneling, and the rate is enhanced on concomitant photobleaching with visible light. Subsequent exposure to UV light (lambda approximately 350-400 nm) converts 6*+ by a 2,3 H-shift to the 1-aminopropene radical cation 7*+, which is confirmed to be the lowest-energy isomer derived from the ionization of either allylamine or cyclopropylamine. Although the parent radical cations of N, N-dimethylallylamine (9*+) and N-methylallylamine (11*+) are both stabilized by the electron-donating character of the methyl group(s), the photobleaching of 9*+ leads to the remarkable formation of the cyclic 1-methylpyrrolidine radical cation 10*+. The first step of this transformation now involves the migration of a hydrogen atom to C2 of the allyl group from one of the methyl groups (rather than from C1); the reaction is then completed by the cyclization of the generated MeN + (=CH2) CH2CH2CH2* distonic radical cation, possibly in a concerted overall process. In contrast to the ubiquitous H-atom transfer from carbon to nitrogen that occurs in the parent radical cations of saturated amines, the alternate rearrangements of either 1b*+ or 5*+ to an ammonium-type radical cation by a hypothetical H-atom shift from C1 to the ionized NH2 group are not observed. This is in line with calculations showing that the thermal barrier for this transformation is much higher (approximately 120 kJ mol-1) than those for the conversion of 1b*+ --> 2*+ and 5*+--> 6*+ (approximately 40-60 kJ mol-1).     

Sensitivity of redox reactions of dyes to variations of conditions created in mass spectrometric experiments

Redox behaviour of four imidazophenazine dye derivatives under mass spectrometric conditions of matrix-assisted laser desorption/ionization (MALDI), laser desorption/ionization (LDI) from metal and graphite surface, electrospray, low temperature secondary ion mass spectrometry (LT SIMS) and fast atom bombardment (FAB) was studied and distinctions in the reduction-dependent spectral patterns were analyzed from the point of view of different quantities of protons and electrons available for reduction in different techniques. The reduction products [M + 2H](+*), [M + 3H](+) and M(-*), [M + H](-) were observed in the positive and negative ion modes, respectively, which permitted to suggest independent occurrence of reduction and protonation/deprotonation processes. LDI from graphite substrate was the only technique that allowed us to obtain abundant negative ions of all dye derivatives. The yield of field ionization (FI) or field desorption (FD) mechanism to ion formation under LDI from rough graphite surface has been addressed. The sensitivity of reduction of the dyes to variation of reduction-initiating agents confirms high redox activity of the dyes essential for their functioning in natural and artificial systems.     

Stroboscopic XMCD-PEEM imaging of standing and propagating spinwave modes in permalloy thin-film structures

Using synchrotron-based stroboscopic photoemission electron microscopy with X-ray circular dichroism as contrast method, we have investigated the high-frequency response of permalloy thin-film structures. Standing precessional modes have been studied in rectangular elements (16 × 32 μm², 10 nm thick) with a high time resolution of about 15 ps in the low-α mode of BESSY. With increasing amplitude of the applied magnetic AC field the particle is driven from an initial symmetric Landau flux-closure state into an asymmetric state and finally into a single-domain state magnetized perpendicular to the applied field H_AC. The electromagnetic microwave field thus can induces a net magnetization in a small particle. This behaviour is a result of the constant throughput of energy (open system) that allows for an increase of local order, contrary to the usual increase on entropy in closed systems. A propagating spinwave in an ultrathin elliptical particle (semi axes 6 × 12 μm², 3 nm thick) was observed in a snapshot series with 25 ps time increment. The phase front of the spinwave with large precessional angle (bright contrast) propagates with a velocity of 8100 m/s, i.e. much faster than typical domain wall velocities in permalloy.     

Bromoplumbate mit kettenförmigen und isolierten Anionen: (Bzl4P)2[Pb3Br8], (Bzl4P)2[Pb3Br8(dmf)2], (Bzl4P)[PbBr3], (Bzl4P)2[PbBr4] und (Bzl4P)4[Pb2Br6][PbBr4]

Bromoplumbates with One‐dimensional Polymeric and Isolated Anions: (Bzl₄P)₂[Pb₃Br₈], (Bzl₄P)₂[Pb₃Br₈(dmf)₂], (Bzl₄P)[PbBr₃], (Bzl₄P)₂[PbBr₄], and (Bzl₄P)₄[Pb₂Br₆][PbBr₄] PbBr₂ reacts with LiBr and (Bzl₄P)(PF₆) (Bzl = CH₂C₆H₅) in acetone to form a series of bromoplumbate complexes with compositions and structures depending on the conditions of reaction and crystallization. While the anions in (Bzl₄P)₂[Pb₃Br₈] ( 1 ) and (Bzl₄P)[PbBr₃] ( 2 ) are one‐dimensional polymers with penta‐ and hexacoordinated Pb atoms, the metal atoms in the mono‐ and dinuclear complex anions of (Bzl₄P)₂[PbBr₄] · 2acetone ( 3 · 2acetone) and (Bzl₄P)₄[Pb₂Br₆][PbBr₄] ( 4 ) bind to four bromo ligands. From DMF as a solvent (Bzl₄P)₂[Pb₃Br₈(dmf)₂] ( 1 b ) crystallizes with the same bromoplumbate structure as in 1 a , but with dmf ligands occupying the coordination sites vacant in 1 a . Upon radiation of compound 3 with ultraviolet light greenish yellow photoluminescence (emssion maximum at 547 nm) is observed. Crystallographic details see “Inhaltsübersicht”.     

Inclusion compounds ofcis-syn-cis andcis-anti-cis diastereoisomers of dicyclohexano-18-crown-6 with amidosulfuric acid

Both title complexes were prepared by reacting a methanol solution of the respective isomer of dicyclohexano-18-crown-6 (DCH18C6) with an aqueous solution of amidosulfuric acid. Crystals suitable for X-ray crystallography were obtained by recrystallization from methanol.Crystals of [cis-syn-cis-DCH18C6][NH₂SO₂OH·CH₃OH] (1) are monoclinic, space groupP2₁ln,a = 21.700(8),b = 13.725(5),c = 9.118(6) Å, = 76.29(2) Å. Refinement led to a final conventionalR value of 0.065 for 2083 reflections. [Cis-anti -cis-DCH18C6][NH₂SO₂OH] (2) crystallizes in the orthorombic space groupPna2₁ with unit cell dimensionsa = 17.154(7),b = 16.051(7),c =8.630(5) Å. Refinement was terminated at anR value of 0.067 for 1936 reflections.     

Two‐Step Spin Transition in a 1D FeII 1,2,4‐Triazole Chain Compound

A thermochromic 1D spin crossover coordination (SCO) polymer [Fe(βAlatrz)₃](BF₄)₂ ? 2 H₂O ( 1? 2 H₂O), whose precursor βAlatrz, (1,2,4‐triazol‐4‐yl‐propionate) has been tailored from a β‐amino acid ester is investigated in detail by a set of superconducting quantum interference device (SQUID), ⁵⁷Fe Mössbauer, differential scanning calorimetry, infrared, and Raman measurements. An hysteretic abrupt two‐step spin crossover (T_1/2^↓=230 K and T_1/2^↑=235 K, and T_1/2^↓=172 K and T_1/2^↑=188 K, respectively) is registered for the first time for a 1,2,4‐triazole‐based Fe^II 1D coordination polymer. The two‐step SCO configuration is observed in a 1:2 ratio of low‐spin/high‐spin in the intermediate phase for a 1D chain. The origin of the stepwise transition was attributed to a distribution of chains of different lengths in 1? 2 H₂O after First Order Reversal Curves (FORC) analyses. A detailed DFT analysis allowed us to propose the normal mode assignment of the Raman peaks in the low‐spin and high‐spin states of 1? 2 H₂O. Vibrational spectra of 1? 2 H₂O reveal that the BF₄^? anions and water molecules play no significant role on the vibrational properties of the [Fe(βAlatrz)₃]²⁺ polymeric chains, although non‐coordinated water molecules have a dramatic influence on the emergence of a step in the spin transition curve. The dehydrated material [Fe(βAlatrz)₃](BF₄)₂ ( 1 ) reveals indeed a significantly different magnetic behavior with a one‐step SCO which was also investigated.     

Role of Hydrogen‐Bonding Acceptors in Organo‐Enamine Catalysis

A hydrogen bond acceptor plays an important role in the catalytic cycle of organo‐enamine catalysis. It can effectively influence the rate of reaction through hydrogen bonding interaction with enammonium (N‐protonated enamine intermediate). Our findings are supported by both kinetic experiments and quantum chemical calculations.