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Methods for the detection of reactive intermediates such as transient radicals are important in organic chemistry, polymer chemistry, biology or medicine. Along these lines we recently reported that 1,5-diphenyl-6-oxo verdazyl radicals can be used as fluorescent spin sensors. In situ generated C-centered radicals are efficiently trapped by the verdazyls, which in turn undergo transformation from a paramagnetic non-fluorescent state to a diamagnetic fluorescent state. Whereas the N-phenyl substituent in the spin probes is of high importance for obtaining profluorescent behavior, the effect of the C(3)-substituent has not been investigated to date. We herein present the synthesis and characterization of various 1,5-diphenyl-6-oxo-verdazyl radicals bearing differently hybridized C-substituents at the C(3) position. Steady-state and time-resolved fluorescence spectroscopy in solution and in the solid state along with time-dependent density functional theory (TDDFT) calculations reveal that a C(3)-aryl substituent is crucial for obtaining fluorescence after spin trapping. In addition, it is shown that the emission wavelength of the C(3)-aryl substituted verdazyl derivatives can be tuned by selective destabilization of the HOMO and the LUMO.

Four new MPtAl 2 (M=Ca, Sr, Ba, Eu) compounds, adopting the orthorhombic MgCuAl 2 -type structure, have been synthesized from the elements using tantalum ampoules. All compounds are obtained as platelet-shaped crystallites and exhibit an increasing moisture sensitivity with increasing size of the formal M cation. Structural investigations indicate a pronounced elongation of the crystallographic b-axis, which results in a significant distortion of the [PtAl 2 ] δ- polyanion. Within the polyanion, layer-like arrangements can be found with bonding Pt-Al interactions within the slab; the increase of the b-axis can be attributed to increasing Al-Al distances and therefore decreasing interactions between the slabs, caused by the differently-sized formal M cations. While the alkaline earth (M=Ca, Sr) representatives exhibit Pauli paramagnetism, BaPtAl 2 shows diamagnetic behavior, finally EuPtAl 2 is ferromagnetic with T C =54.0(5) K. The effective magnetic moment indicates that the Eu atoms are in a divalent oxidation state, which is confirmed by 151 Eu Mössbauer spectroscopic investigations. Measurements below the Curie-temperature show a full magnetic hyperfine field splitting with B hf =21.7(1) T. 27 Al and 195 Pt magic-angle spinning NMR spectroscopy corroborates the presence of single crystallographic sites for the Pt and Al atoms. The large 27 Al nuclear electric quadrupolar coupling constants confirm unusually strong electric field gradients, in agreement with the structural distortions and the respective theoretical calculations. X-ray photoelectron spectroscopy has been utilized to investigate the charge transfer within the polyanion. The Pt 4f binding energy decreases with decreasing electronegativity / ionization energy of the alkaline earth elements, suggesting an increasing electron density at the Pt atoms. Theoretical investigations underline the platinide character of the investigated compounds by Bader charge calculations. The analysis of the integrated crystal orbital Hamilton population (ICOHP) values, electron localization function (ELF) and isosurface analyses lead to a consistent structural picture, indicating stable layer-like arrangements of the [PtAl 2 ] δ- polyanion., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A total of 35 intermetallic aluminum compounds have been synthesized from the elements via arc melting and characterized by powder X-ray diffraction. A total of 15 of them have been previously reported; however, detailed property investigations were missing. Compounds of the RETMAl 2 (rare earth metal RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu) series with transition metal TM = Ni, Pd, and Pt crystallize isostructurally in the orthorhombic MgCuAl 2 type structure ( Cmcm, oC16, fc 2 ). Single-crystal X-ray diffraction investigations were conducted on YNiAl 2 , LaNiAl 2 , YPdAl 2 , ScPtAl 2 , and YPtAl 2 . The TM and Al atoms form a [TMAl 2 ] δ- polyanion, the RE atoms reside in cavities within the framework. While the Sc, Y, La, and Lu compounds exhibit Pauli-paramagnetic behavior, consistent with all atoms being closed shell, the other RETMAl 2 compounds show paramagnetism along with magnetic ordering at low temperatures, in line with an open-shell trivalent oxidation state for the RE atoms. Solid-state 27 Al NMR investigations were carried out on the Pauli-paramagnetic samples, all showing only a single central transition, in line with one crystallographic site for the respective atoms. The observed quadrupolar coupling constants and electric-field-gradient asymmetry parameters were found to be in good agreement with the density-functional-theory-calculated values. Isotropic resonance shifts are dominated by the Fermi-contact interactions with s-conduction electron densities at the Fermi edge (Knight shifts). The bonding characteristics mirror the electronic density of states and crystal chemistry of the family of intermetallic compounds under consideration. Both the Knight shifts and quadrupolar coupling constants can be predicted based on element-specific increments.

The YCrB4 type borides YTB4 (T = Mo, W, Re) were synthesized from the elements by arc-melting and subsequent annealing. The structures were refined from single crystal X-ray diffractometer data: Pbam, a = 602.84(8), b = 1164.5(1), c = 361.20(4) pm, wR2 = 0.0404, 624 F2 values, 26 variables for YMoB4, a = 603.00(7), b = 1165.1(1), c = 360.63(6) pm, wR2 = 0.0487, 474 F2 values, 26 variables for YWB4, and a = 596.67(6), b = 1154.4(1), c = 360.21(4) pm, wR2 = 0.0465, 544 F2 values, 26 variables for YReB4. The boron atoms build up planar networks which are a tessellation of slightly distorted pentagons and heptagons. Adjacent networks coordinate the transition metal and yttrium atoms in the form of pentagonal and heptagonal prisms, respectively. The four crystallographically distinct boron sites are differentiated by high-resolution 11B solid state isotropic magnetic shifts and nuclear electric quadrupolar coupling constants. Partial site assignments are possible based on comparisons with electric field gradient calculations using the WIEN2k code. 89Y MAS NMR spectroscopic studies suggest substantially weaker Knight shift contributions to the resonance frequencies when compared to other intermetallic yttrium compounds, including other ternary yttrium boride compounds measured previously.

Antiferromagnetic coupling in TEMPO-based radicals can be enhanced via self-assembly through London dispersion interactions in amphiphilic solids. The synthesis, magnetic characterization, and three crystal structures of the solid radical ion salts (R-DMAT-n)X with various counterions X and alkyl chain lengths n are reported. Magnetic susceptibility and absolute EPR signal intensity measurements show singlet-triplet transitions in a number of cases, which is discussed in relation to the crystal structures. Antiferromagnetic ordering effects are sensitive to both the length of the alkyl chain and the counter anion.

The silicide Sc 5 Pd 4 Si 6 was synthesized from the elements by arc-melting. Its structure was refined from single crystal X-ray diffractometer data: Immm, Li 5 Cu 3.75 P 6 type, a = 397.12(6), b = 945.4(1), c = 1314.4(2) pm, wR 2 = 0.0245, 578 F 2 values and 29 parameters. The palladium atoms have slightly distorted tetrahedral silicon coordination and a condensation of these PdSi 4 tetrahedra leads to a two-dimensional substructure which is condensed via Si 2 pairs (234 pm Si-Si), forming the [Pd 4 Si 6 ] δ- polyanionic network. The Sc 5 Pd 4 Si 6 structure contains three crystallographically independent scandium sites with coordinations Sc1@Pd 4 Si 8 Sc 6 , Sc2@Pd 6 Si 6 Sc 3 and Sc3@Pd 4 Si 6 Sc 4 . Sc 5 Pd 4 Si 6 is a Pauli paramagnet with a low susceptibility of 2.9(5) × 10 -5 emu mol -1 at room temperature. The 29 Si MAS-NMR spectrum confirms the presence of two crystallographically distinct sites in a 2 : 1 ratio. Likewise, the three crystallographic scandium sites are well-differentiated by three 45 Sc MAS NMR signals in the expected 2 : 2 : 1 ratio. Unambiguous assignments could be made based on the comparison of the nuclear electric quadrupolar coupling parameters with predicted values from WIEN2k calculations.

In this study, we address the question of the origin of ferromagnetic or antiferromagnetic interactions in alkynyl-substituted 1,5-diphenyl-6-oxo verdazyl radicals. While a TMS-alkynyl derivative (3) shows antiferromagnetic ordering at low temperatures, the corresponding deprotected alkynyl verdazyl (4) shows ferromagnetic interactions. For both compounds, magnetic Heisenberg chains are characteristic, which were studied systematically by means of X-ray crystallography and quantum chemical calculations. Ferromagnetic interactions are rarely found in such radicals. Therefore, uncovering such structure-property relationships is of crucial importance in order to understand and design promising ferromagnetic networks. Using this knowledge, we were able to design and crystallize diyne derivatives showing comparable solid state characteristics and therefore antiferro- and ferromagnetic Heisenberg chain structures. We show that the understanding of such property-structure relationships is adequate for the design of organic-magnetic materials with defined cooperative effects within the class of verdazyl radicals.

We present an efficient and accurate computational procedure to calculate properties measurable by EPR spectroscopy. We simulate a molecular dynamics (MD) trajectory by employing the quantum mechanically derived force field (QMDFF) [S. Grimme, J. Chem. Theory Comput., 2014, 10, 4497] and sample the trajectory at different time steps. For each snapshot EPR properties are calculated with a hybrid density functional theory (DFT) method. EPR spectra are simulated based on the averaged results. We applied the strategy to a number of previously published and novel verdazyl radicals, for which we recorded EPR spectra. The resulting simulated spectra are compatible with experiment already before employing an additional fitting step, in contrast to those from single point electronic-structure calculations. After the refinement, the experimental data are excellently reproduced, and the fitted EPR parameters do not deviate much from the calculated ones. This provides confidence in ascribing a direct physical meaning to the refined data in terms of experimental EPR parameters rather than merely considering them as mathematical fit parameters. We also find that couplings to hydrogen nuclei have a significant influence on the spectra of verdazyl radicals.

The reduction of the tribromoamidosilane {N(SiMe 3 )Dipp}SiBr 3 (Dipp=2,6-iPr 2 C 6 H 3 ) with potassium graphite or magnesium resulted in the formation of [Si 4 {N(SiMe 3 )Dipp} 4 ] (1), a bicyclo[1.1.0]tetrasilatetraamide. The Si 4 motif in 1 does not adopt a tetrahedral substructure and exhibits two three-coordinate and two four-coordinate silicon atoms. The electronic situation on the three-coordinate silicon atoms is rationalized with positive and negative polarization based on EPR analysis, magnetization measurements, and DFT calculations as well as 29 Si CP MAS NMR and multinuclear NMR spectroscopy in solution. Reactivity studies with 1 and radical scavengers confirmed the partial charge separation. Compound 1 reacts with sulfur to give a novel type of silicon sulfur cage compound substituted with an amido ligand, [Si 4 S 3 {N(SiMe 3 )Dipp} 4 ] (2)., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Bifunctional mesoporous silica was prepared by co-condensation of tetraethyl orthosilicate (TEOS) with functionalized organosilanes containing azides or alkoxyamines. Orthogonal functional groups at the particles were selectively addressed in subsequent chemical modifications through "click"-chemistry ("click to ligand" strategy) and radical nitroxide exchange. Palladation with PdCl 2 delivered Pd nanoparticle-loaded silica material bearing sulfoxides and additional aminoamides as stabilizing ligands by means of in situ reduction of the Pd II -salt. These functional particles were successfully applied to the hydrogenation of alkynes and alkenes. Aldehyde hydrodeoxygenation and benzyl ether cleavage were achieved with these hybrid catalysts under mild conditions. Particles were analyzed by IR, TEM/STEM, EDX, and solid-state NMR spectroscopy., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

New P/N-containing π-electron systems comprising fully planar biaryl arrays are synthesized by multiple radical phosphanylation. The biaryl moiety in these highly strained planar π-systems is rigidified by double P-bridging. The electronic properties of the core biaryl entity are varied by introducing N-donor substituents or by installing N-atoms within the π-system, thereby moving to the viologen core structure. The electrochemical and photophysical properties of these compounds are discussed and compared with those of related systems., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report on a series of eight diaryl-6-oxo-verdazyl radicals containing a tert-butyl group at the C(3) position with regard to their crystal structure and magnetic properties by means of magnetic susceptibility measurements in combination with quantum chemical calculations using a first-principles bottom-up approach. The latter method allows for a qualitative prediction and detailed analysis of the correlation between the solid-state architecture and magnetic properties. Although the perturbation in the molecular structure by varying the substituent on the N-aryl ring may appear small, the effects upon the structural parameters controlling intermolecular magnetic coupling interactions are strong, resulting in a wide spectrum of cooperative magnetic behavior. The non-substituted 1,5-diphenyl-tert-butyl-6-oxo-verdazyl radical features a ferromagnetic one-dimensional spin ladder type magnetic network-an extremely rarely observed phenomenon for verdazyl radicals. By varying substituents at the phenyl group, different non-isostructural compounds were obtained with widely different magnetic motifs ranging from linear and zigzag one-dimensional chains to potentially two-dimensional networks, from which we predict magnetic susceptibility data that are in qualitative agreement with experiments and reveal a large sensitivity to packing effects of the molecules. The present study advances the fundamental understanding between solid-state structure and magnetism in organically based radical systems., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Gold nanoparticles (AuNPs) are subjects of broad interest in scientific community due to their promising physicochemical properties. Herein we report the facile and controlled light-mediated preparation of gold nanoparticles through a Norrish type I reaction of photoactive polymers. These carefully designed polymers act as reagents for the photochemical reduction of gold ions, as well as stabilizers for the in situ generated AuNPs. Manipulating the length and composition of the photoactive polymers allows for control of AuNP size. Nanoparticle diameter can be controlled from 1.5 nm to 9.6 nm., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis and characterization of various 6-oxo-verdazyl radicals and their diamagnetic styryl radical trapping products are presented. It is shown that styryl radical trapping products derived from N -phenyl verdazyls show fluorescence whereas the N -methyl congeners are non-fluorescent. In the parent N -phenyl verdazyls fluorescence is fully quenched which renders these compounds highly valuable profluorescent radical probes.