Synthesis and Optical Properties of Water‐Soluble Polyglycerol‐Dendronized Rylene Bisimide Dyes

Four new water‐soluble polyglycerol‐dendronized perylene, terrylene, and quaterrylene bisimides have been synthesized and characterized with respect to their optical properties in polar organic solvents and water by using UV/Vis and fluorescence spectroscopy. All of these dyes were highly soluble in water, but the size of the chosen polyglycerol dendron was only sufficient to completely suppress dye aggregation for the core‐unsubstituted perylene derivative. Their high solubility in water and their absorption and emission wavelengths up to the NIR region make the core‐unsubstituted perylene and terrylene bisimides ideal candidates for applications in bioimaging, whilst the lack of fluorescence for quaterrylene bisimide in all polar solvents does not warrant further investigation of this chromophore in fluorescence and imaging applications. Likewise, tuning of the emission of rylene bisimides towards longer wavelengths by employing electron‐donating bay substituents is not a promising strategy, owing to the lower fluorescence quantum yields in polar solvents and, in particular, in water.     

Dendritic aliphatic polyethers as high-loading soluble supports for carbonyl compounds and parallel membrane separation techniques

This paper describes the use of dendritic polyglycerol as a new high-loading polymeric support. The soluble polyether skeleton allows the parallel synthesis of small libraries on a large scale (1-5 mmol). Purification of polymer-bound products is easily achieved by a parallel dialysis apparatus, which was developed to separate up to 12 reaction mixtures simultaneously. The terminal 1,2-diol groups of polyglycerol (loading capacity: 4.1 mmol diol/g) can be directly coupled with carbonyl compounds without additional linker groups. At the same time the polyglycerol support acts as a polymeric ketal protecting group. The coupling of the carbonyl compounds occurs in high yields, and effective loading capacities of up to 3.5 mmol of ketone/g can be reached. The obtained polymeric acetals can easily be characterized by standard analytical techniques, such as NMR, IR, UV, and SEC. The versatility of this new polymeric support for solution-phase organic synthesis is demonstrated by two efficient polymer-supported syntheses: nucleophilic substitutions of gamma-chloroketones with amines and Suzuki-coupling on p-bromobenzaldehyde. The acid-catalyzed acetal cleavage with a solid-phase acidic ion-exchange resin in methanol demonstrates the orthogonal use of these soluble polymeric supports with conventional solid-phase reagents. Cleavage of products occurs in high yields, and almost complete recovery (>95%) of the polyglycerol support has been demonstrated after phase separation or ultrafiltration.     

Magnetic and Electrical Properties, Eu Mössbauer Spectroscopy, and Chemical Bonding of REAgMg (RE=La, Ce, Eu, Yb) and EuAuMg

Single-phase samples of REAgMg (RE=La, Ce, Eu, Yb) and EuAuMg were prepared by reacting the elements in sealed tantalum tubes in a high-frequency furnace. LaAgMg and CeAgMg adopt the hexagonal ZrNiAl-type structure, while EuAgMg, YbAgMg, and EuAuMg crystallize with the orthorhombic TiNiSi type. Chemical bonding was exemplarily investigatedfor EuAgMg and EuAuMg on the basis of TB-LMTO-ASAcalculations. Magnetic susceptibility measurements indicatePauli paramagnetism for LaAgMg and YbAgMg with room-temperature susceptibilities of 2.4(1)×10⁻⁹ and 1.5(1)×10⁻⁹ m³/mol, respectively. CeAgMg remains paramagnetic down to 2 K. The experimental magnetic moment of 2.52(2) μ_B/Ce above 50 K is compatible with trivalent cerium. EuAgMg and EuAuMg are paramagnetic above 50 K with experimentalmagnetic moments of 7.99(5) μ_B/Eu for the silver and 7.80(5) μ_B/Eu for the gold compound, indicating divalent europium. Ferromagnetic ordering is detected at T_C=22.0(3) K (EuAgMg) and T_C=36.5(5) K (EuAuMg). At 4.2 K and 5 T the saturation magnetizations are 7.1(1) and 7.3(1) μ_B/Eu for EuAgMg and EuAuMg, respectively. According to the very small hysteresis, EuAgMg and EuAuMg may be classified as soft ferromagnets. All compounds are metallic conductors. For EuAgMg and EuAuMg freezing of spin-disorder scattering is observed below T_C. At 78 K ¹⁵¹Eu Mössbauer spectra show isomer shifts of −9.00(4) and −8.72(8) mm/s for EuAgMg and EuAuMg, respectively. Full magnetic hyperfine field splitting is detected at 4.2 K with hyperfine fields of 17.4(1) and 18.3(2) T at the europium nuclei of EuAgMg and EuAuMg.     

Decomposition of EuPdIn and EuPtIn at high temperature and high pressure—formation of the hexagonal Laves phases EuPd0.72In1.28 and EuPt0.56In1.44

EuPd_0.72In_1.28 and EuPt_0.56In_1.44 were prepared under multianvil high-pressure (10.5 GPa) high-temperature (1500 and 1400 K) conditions from the precursor compounds EuPdIn and EuPtIn. They were investigated by X-ray diffraction on both powders and single crystals: MgZn₂-type, space group P6₃/mmc, a=578.7(1) pm, c=944.9(3) pm, wR2=0.0734, 263 F² values for EuPd_0.72In_1.28 and a=591.1(2) pm, c=933.8(2) pm, wR2=0.0853, 151 F² values for EuPt_0.56In_1.44 with 13 variable parameters per refinement. Both structures are built up from face- and corner-sharing tetrahedra of palladium (platinum) and indium atoms. The europium cations are located in cavities within the three-dimensional [Pd_0.72In_1.28] and [Pt_0.56In_1.44] networks. The 2a and 6 h positions of the tetrahedral networks show mixed Pd/In and Pt/In occupancy in EuPd_0.72In_1.28 and EuPt_0.56In_1.44, respectively. The crystal chemistry of these indides is briefly discussed.     

Direct fission versus sequential evaporation mechanism of sputtered caesium iodide cluster ions

A triple stage hybrid mass spectrometer was scanned for the trapping of the reaction intermediates of the over-all loss of two CsI-moieties from size-selected caesium iodide cluster ions of the general formula Cs (CsI)⁺ _n . In addition to appropriate MS/MS/MS-methods an electrically floated collision cell has been applied to trap intermediates of unimolecular and collision-induced evaporations. In comparison with other experimental findings the features of the evaporation mechanism are discussed.     

Darstellung,Ramanspektren und Kristallstrukturen von V2O3(SO4)2, K[VO(SO4)2] und NH4[VO(SO4)2]

Preparation, Raman Spectra, and Crystal Structures of V₂O₃(SO₄)₂, K[VO(SO₄)₂], and NH₄[VO(SO₄)₂] The oxo-sulfato-vanadates(V) V₂O₃(SO₄)₂, K[VO(SO₄)₂], and NH₄[VO(SO₄)₂] have been prepared as crystals suitable for X-ray structure determination. In all structures sulfate acts as an unidentate ligand only toward a single vanadium atom. The structure of V₂O₃(SO₄)₂ consists of a threedimensional network of pairs of cornershared VO₆ octahedra with one terminal oxygen atom each, and SO₄ tetrahedra. All oxygen atoms of the sulfate ions are coordinated. NH₄[VO(SO₄)₂] and K[VO(SO₄)₂] are isostructural. VO₆ octahedra with one terminal oxygen atom and pairs of sulfate tetrahedra form infinite chains by corner sharing. The chains are weakly interlinked to layers. The sulfate ions are distorted towards planar SO₃ molecules and single oxygen atoms attached to vanadium. This structural detail gives an explanation for the mechanism of the reversible reaction K[VO(SO₄)₂] ? K[VO₂(SO₄)] + SO₃ at 400°C. Raman spectra of the compounds have been recorded and interpreted with respect to their structures. Crystal data: V₂O₃(SO₄)₂, monoclinic, space group P2₁/a, a = 947.2(4), b = 891.3(3), c? 989.1(4) pm, β = 104.56(3)°, Z = 4, 878 unique data, R(R_w) = 0.039(0,033); K[VO(SO₄)₂], orthorhombic, space group P2₁2₁2₁, a = 495.3(2), b = 869.6(9), c = 1 627(1)pm, Z = 4, 642 unique data, R(R_w) = 0,11(0,10); NH₄[VO(SO₄)₂], orthorhombic, space group P2₁2₁2₁, a = 495.3(1), b = 870.0(2), c = 1 676.7(4)pm, Z = 4, 768 unique data, R(R_w) = 0.088(0.083).