Poly[n]prismanes: a family of stable cage structures with half-planar carbon centers

A series of bi[n]prismanes and tri[n]prismanes (n = 3-6) containing n and 2n, respectively, tetracoordinated carbon centers with nonclassical bisphenoidal (half-planar) configuration has been designed computationally.     

Cadmium-Inspired Self-Polymerization of {LnIIICd2} Units: Structure,Magnetic and Photoluminescent Properties of Novel Trimethylacetate 1D-Polymers (Ln = Sm,Eu, Tb,Dy, Ho,Er, Yb)

A series of heterometallic carboxylate 1D polymers of the general formula [Ln^IIICd₂(piv)₇(H₂O)₂]_n·nMeCN (Ln^III = Sm (1), Eu (2), Tb (3), Dy (4), Ho (5), Er (6), Yb (7); piv = anion of trimethylacetic acid) was synthesized and structurally characterized. The use of Cd^II instead of Zn^II under similar synthetic conditions resulted in the formation of 1D polymers, in contrast to molecular trinuclear complexes with Ln^IIIZn₂ cores. All complexes 1–7 are isostructural. The luminescent emission and excitation spectra for 2–4 have been studied, the luminescence decay kinetics for 2 and 3 was measured. Magnetic properties of the complexes 3–5 and 7 have been studied; 4 and 7 exhibited the properties of field-induced single-molecule magnets in an applied external magnetic field. Magnetic properties of 4 and 7 were modelled using results of SA-CASSCF/SO-RASSI calculations and SINGLE_ANISO procedure. Based on the analysis of the magnetization relaxation and the results of ab initio calculations, it was found that relaxation in 4 predominantly occurred by the sum of the Raman and QTM mechanisms, and by the sum of the direct and Raman mechanisms in the case of 7.     

Fluorocarbon crowning: Langmuir-Blodgett deposition versus self-assembly at molecularly rough surfaces

Langmuir-Blodgett deposition of a single monolayer of 1,2,4,5-tetrakis[(N-(perfluoroundecanoamidoethyl)-N,N-dimethylammonium)methyl]benzene tetrabromide (1) onto a thin film made from alternating layers of poly(diallydimethylammonium chloride) (PDADMA) and poly(4-styrenesulfonate) (PSS) ions affords a uniform fluorinated surface of low energy. An analogous surface that has been constructed by self-assembly shows the same critical surface tension of 16.5 dyn/cm. A comparison of Zisman plots for these two modified films, in combination with analysis by X-ray photoelectron spectroscopy, indicates that Langmuir-Blodgett deposition produces a higher quality and more densely packed fluorocarbon surface that is very hydrophobic. In sharp contrast, the use of a single-chain analog (i.e., N-(perfluoroundecanoamidoethyl)-N,N,N-trimethylammonium bromide) (2)) affords relatively high energy surfaces by Langmuir-Blodgett deposition and by self-assembly.     

Novel self-assembling system based on resorcinarene and cationic surfactant

Mixed association of calix[4]resorcinarene with ethyl sulfonate groups on the lower rim and dimethylaminomethyl groups on the upper rim (CR) and cationic surfactant 4-aza-1-hexadecyl-azoniabicyclo[2.2.2]octane bromide (DABCO-16) is studied by methods of tensiometry, conductometry, potentiometry and NMR spectroscopy at fixed CR concentration and varied surfactant concentration. Beyond ca. 0.4 mM of DABCO-16, mixed aggregates enriched by CR are proved to be formed due to electrostatic forces, while beyond ca. 5 mM, aggregates enriched by surfactant occur due to the hydrophobic effect. Spectrophotometry monitoring of the solubilization of a hydrophobic dye, Orange OT, demonstrated that only the second type of mixed aggregate enriched by DABCO-16 is capable of binding the organic probe, while the mixed system where the surfactant is a minor component shows no binding capacity towards Orange OT. This finding can be used for the design of nanocontainers with controllable binding/release properties.     

Fluorescent Silver Nanoclusters in Condensed DNA

We study the formation and fluorescent properties of silver nanoclusters encapsulated in condensed DNA nanoparticles. Fluorescent globular DNA nanoparticles are formed using a dsDNA–cluster complex and polyallylamine as condensing agents. The fluorescence emission spectrum of single DNA nanoparticles is obtained using tip‐enhanced fluorescence microscopy. Fluorescent clusters in condensed DNA nanoparticles appear to be more protected against destructive damage in solution compared to clusters synthesized on a linear polymer chain. The fluorescent clusters on both dsDNA and ssDNA exhibit the same emission bands (at 590 and 680 nm) and the same formation efficiency, which suggests the same binding sites. By using density functional theory, we show that the clusters may bind to the Watson–Crick guanine–cytosine base pairs and to single DNA bases with about the same affinity.     

Spin Exchange Between Charged Paramagnetic Particles in Dilute Solutions

Kinetic equations for the spin density matrix which take into account binary collisions and a method of calculating the spin exchange effective radius have been generalized to the case of dilute solutions of charged paramagnetic particles. The effective radius of the spin exchange and rate constant of the bimolecular spin exchange between charged paramagnetic particles in solutions have been calculated numerically. Calculations have been performed under the assumption that the exchange interaction is isotropic and decays exponentially with the increase in the distance between radicals, and the solution has a given dielectric permittivity and Debye screening radius. Dependences of the spin exchange rate constant on the mutual diffusion coefficient, exchange and electrostatic interactions parameters have been found numerically. The theory has been applied to experimental results taken from the literature. The rate constant of the spin exchange between radicals of like charge found from the experiment and calculated within the developed theory are in good qualitative agreement .     

A new class of binuclear and trinuclear iron-sulfur clusters derived from bis[bis(trimethylsilyl)amido]iron(II)

The compound Fe[N(SiMe 3) 2] 2 is shown to be a useful precursor to dinuclear and trinuclear iron-sulfur-silylamido complexes by reaction with thiols or thiols and sulfur in tetrahydrofuran (THF) or toluene. Reaction with 1 equiv of p-tolylthiol affords [Fe 2(mu 2-S- p-tol) 2(N(SiMe 3) 2) 2(THF) 2] ( 1); with 0.5 equiv of adamantane-1-thiol, [Fe 2(mu 2-S-1-Ad)(mu 2-N(SiMe 3) 2)(N(SiMe 3) 2) 2] ( 2) is formed. The clusters [Fe 3(mu 3-Q)(mu 2-SR) 3(N(SiMe 3) 2) 3] are available by three methods: (i) self-assembly in the systems Fe[N(SiMe 3) 2] 2/RSH/S or Se [Q = S, R = p-tol ( 3) and 1-Ad ( 5)]; (ii) reaction of 1 with Q = S or Se to yield 3 or [Fe 3Se(S- p-tol) 3(N(SiMe 3) 2) 3] ( 4); (iii) reaction of 2 with 1-AdSH and S to give 5. Structures of 1- 5 are presented. Complexes 1 and 2 contain planar Fe 2S 2 and Fe 2SN rhombs. Clusters 3- 5 contain a mixed-valence Fe 3Q(SR) 3 core with trigonal (cuboidal) geometry. Of known iron-sulfur clusters, these most closely resemble previously reported [Fe 3S(S-R-S) 3] (2-) stabilized by bidentate thiolate ligands. Complexes 1- 5, together with a small set of recently described clusters of nuclearities 2, 4, and 8, constitute a new class of iron-sulfur-silylamido clusters. Complexes 3- 5 constitute a new structure type of mixed-valence iron-sulfur clusters.     

Expanded bodipy dyes: anion sensing using a bodipy analog with an additional difluoroboron bridge

Oxalyl-tethered pyrroles can be doubly bridged with two difluoroboron chelating units to yield bright orange dyes. Interestingly, in polar organic solvents, the addition of fluoride and cyanide result in reversible detachment of the otherwise stable difluoroboron bridges, resulting in sharp changes in color. Thus, this novel compound behaves as a highly selective chromogenic sensor for fluoride and cyanide ions.     

Synthesis of amorphous carbon nanoparticles and carbon encapsulated metal nanoparticles in liquid benzene by an electric plasma discharge in ultrasonic cavitation field

A newly-developed method permits an electric plasma discharge to occur with relatively low electric power in insulating organic solutions due to the presence of an ultrasonic cavitation. A stable electric plasma could be generated in an ultrasonic cavitation field containing a thousand tiny activated bubbles, in which the electric conductivity could be improved due to formed radicals and free electrons, using copper electrodes and a titanium ultrasonic horn. This method allowed us to synthesize pyrolytic amorphous carbon nanoparticles smaller than about 30 nm in diameter from benzene liquid. In addition, we synthesized TiC nanoparticles about 50-150 nm in size, and copper nanoparticles smaller than 10 nm, which were encapsulated in multilayered graphite cages. Finally, we used GC-MS and MALDI-TOF-MS to observe and analyze the polymerized compounds and the degree of polymerization of the benzene liquid after the plasma treatment.     

Molecular flexibility as a factor affecting the surface ordering of organic adsorbates on metal substrates

The effect of molecular flexibility on the surface ordering of complex organic adsorbates is explored, using alpha,omega-dihexylquaterthiophene (DH4T) and mixed DH4T|tetracene phases on Ag(111) as model systems. The structure of DH4T/Ag(111) interfaces is determined by the flexibility of the hexyl chains at either end of the quaterthiophene backbone: Above 273 K, DH4T forms a nematic liquid crystalline phase with a director close to the [112] direction of the silver substrate. At 273 K, a reversible phase transition to a long-range ordered, point-on-line coincident phase is observed. However, this ordered state is still affected substantially by the flexible nature of DH4T, which materializes in a large number of local structural defects. If traces of DH4T are coevaporated with tetracene, inclusions of a 1:1 stoichiometric DH4T|tetracene phase are found in a tetracene/Ag(111) matrix (alpha-phase). In this mixed phase, the two surface enantiomers of pro-chiral DH4T on one hand and tetracene on the other form a complex stripe structure. The mixed phase shows a higher degree of order than present at the pure DH4T/Ag(111) interface, which also lacks chiral organization. The addition of tetracene molecules as structural templates stabilizes certain conformations of DH4T and thus, by balancing its structural flexibility, allows the surface-induced chirality of DH4T to become a decisive factor in determining the structure of the mixed phase.