Synchronized picosecond pulse generation with a synchronously pumped dye laser and a compressed Nd: YAG laser for non-degenerate transient grating experiments

We have set up a laser system which simultaneously provides synchronized picosecond pulses in the visible and at a wavelength of 1.06 m with a repetition rate of 76 MHz. The set-up consists of a dye laser synchronously pumped by the second harmonic of a cw mode-locked Nd:YAG laser and a fiber-grating compressor for the fundamental wavelength of the Nd;YAG laser. Crosscorrelation measurments reveal the time jitter between the two pulse trains to be less than 10 ps. As a first application we have performed non-degenerate transient grating experiments in semiconductors. The non-degenerate technique allows to use excitation energies well above the bandgap energy and to separate non-linear refractive index effects from photoinduced absorption or transmission changes.     

Syntheses of a Cp'Re=S derivative and more complex products

The reaction of Cp'ReCl(2)S(3) (Cp' = Me(4)EtC(5)) with slightly less than 2 equiv of a phosphine reagent results in the formation of [Cp'Re(Cl)(2)(mu-S)](2), 2, which has been characterized by an X-ray diffraction study. Reactions of 2 with nucleophiles did not lead to monomeric derivatives of the type Cp'ReS(Cl)(2)(Nuc). The reaction of Cp'ReCl(2)(SC(2)H(4)S) with (Me(3)Si)(2)S resulted in the formation of three new products: Cp'ReS(SC(2)H(4)S), 4; Cp'Re(S(3))(SC(2)H(4)S), 5; and a tetranuclear derivative, [(Cp'Re)(2)(mu-S)(mu,eta(2)-SC(2)H(4)S)(mu,eta(1)-SC(2)H(4)S](2)Cl(2), 6. Complexes 4 and 6 have been characterized by X-ray diffraction studies. The electrochemical properties of the mononuclear Re=S derivative, 4, are compared with those of Re=O and Re=NR analogues.     

Synthesis and structure of trigonal and tetragonal connectors for a "Tinkertoy" construction set

We describe a convergent synthesis of eight 1,3,5- and 1,2,4,5-substituted benzene derivatives with long rigid arms containing 4-pyridyl, 2,2'-bipyridyl, and 2,2'-bipyrimidyl termini, meant to be used as trigonal or tetragonal connectors for the construction of large molecular structures. The synthesis involved copper-free Pd-mediated coupling of terminal acetylenes to aryl halides. First, one of the termini of 1,3-diethynylbicyclo[1.1.1]pentane was coupled with a brominated aza heterocycle, and second, 3 equiv of the resulting extended arm were coupled with 1,3,5-triiodobenzene or 4 with 1,2,4,5-tetraiodobenzene. An improved large-scale synthesis for 1,3-diethynylbicyclo[1.1.1]pentane is described. The structures of two of the arms were determined by single-crystal X-ray analysis. Several long molecular rods with 4-pyridyl termini were obtained as byproducts, and a single-crystal X-ray structure is reported for the shortest of these.     

Reactions of dithiolate ligands in mononuclear complexes of rhenium(V)

The thermal reactions of the Re(V) dithiolate complex Cp'ReCl2(SCH2CH2S), 1 (where Cp' = EtMe4C5), and related derivatives have been studied. When 1 is heated in toluene in a sealed evacuated tube at 100 degrees C, a dehydrogenation reaction occurs to form a new rhenium complex with a dithiolene ligand, Cp'ReCl2(SCHCHS), 6, in ca. 40% yield. The structure of 6 has been confirmed by an X-ray diffraction study. Under the thermal conditions studied, 1 also undergoes an olefin extrusion reaction. Free ethene is detected in the NMR spectrum of the products, and insoluble rhenium products are also formed. When 1 is reacted with excess ethene under mild conditions, a new organic product, 1,4-dithiane, is formed. Complex 1 is also found to react with oxidants, such as O2 and S8, under mild conditions to form the dehydrogenation product 6. Kinetic studies of the thermal reaction of 1 and related derivatives have been completed, and possible mechanisms for the thermally induced dehydrogenation reaction are discussed.     

Structural and Spectroscopic Characterization of Iron(III) Dioxoporphodimethene Complexes and Their Autoreduction to an Iron(II) Complex in Pyridine

Three iron complexes of the meso-dioxo derivative of octaethylporphryin (trans-H(2)OEPO(2)) were characterized by X-ray diffraction. Green ClFe(III)(trans-OEPO(2)).1.5C(6)H(6) crystallizes in the monoclinic space group P2(1)/c with a = 13.766(3) ?, b = 19.075(3) ?, c = 15.217(3) ?, beta = 99.87(2) degrees at 123 K with Z = 4. Refinement of 2712 reflections with F > 6.0sigma(F) and 223 parameters yielded R = 0.0624, R(w) = 0.0596. The iron complex contains a domed dioxoporphodimethene macrocyclic ligand. The observation of a five-coordinate iron(III) ion with an axial Fe-Cl distance of 2.232(2) ? and in-plane Fe-N distances averaging 2.082 ? is consistent with its high-spin (S = (5)/(2)) character. This monomer is readily converted to the green {Fe(III)(trans-OEPO(2))}(2)O using aqueous hydroxide. {Fe(III)(trans-OEPO(2))}(2)O crystallizes in the monoclinic space group C2/c with a = 23.541(8) ?, b = 15.392(5) ?, c = 18.686(8) ?, and beta = 90.09(3) degrees at 294 K with Z = 8. Refinement of 3472 reflections with F > 6.0sigma(F) and 393 parameters yielded R = 0.0484, R(w) = 0.0527. The complex possesses a crystallographically imposed 2-fold symmetry axis that passes through the oxo ligand. The dioxoporphodimethene ligands within the molecule are roof-shaped and fold away from each other. The axial Fe-O distance is 1.749(1) ? with longer in-plane Fe-N distances (average 2.077 ?). The Fe-O-Fe angle of 165.4(2) degrees deviates significantly from linearity and is more acute than related porphyrin complexes. Pyridine solutions of either the iron(III) monomer or &mgr;-oxo dimer autoreduce over a period of days to give (py)(2)Fe(II)(trans-OEPO(2)). This red compound crystallizes in the space group P2(1) with a = 19.177(4) ?, b = 20.039(4) ?, c = 10.547(2) ?, and beta = 100.36(3) degrees at 130 K with Z = 2. Refinement of 5090 reflections with one restraint and 984 parameters yielded R1 = 0.0684, wR2 = 0.1763. The complex crystallizes with two distinct molecules in the asymmetric unit; each molecule contains a different degree of disorder with respect to the trans meso oxygen atoms (50/50, 71/29). Each independent molecule exhibits severe ruffling of the macrocycle. The six coordinate iron(II) center is diamagnetic. The axial Fe-N(pyridine) distances average 1.98 ?, and the in-plane Fe-N(pyrrole) distances average 1.95 ?. A common trend observed for the dioxoporphodimethene macrocycle in all of these structures is an elongation toward the trans oxidized meso carbons. These complexes were originally prepared as cis and trans isomeric mixtures that can be enriched in the trans isomer by fractional crystallization. This is evident in their distinctive (1)H NMR spectra. In addition, these compounds are characterized by electron impact mass spectrometry and UV-visible, ESR, and infrared spectroscopies.     

Proton-mediated electron configuration change in high-spin iron(II) porphyrinates

The synthesis, molecular structure, and electronic structure characterization of two five-coordinate high-spin imidazolate-ligated iron(II) porphyrinates are reported. Their electronic structure, as deduced from M?ssbauer spectra obtained in strong magnetic fields, is distinctly different from that of the analogous imidazole-ligated species. The resulting electronic structure models are consistent with all observed differing features in the two classes.     

Comprehensive thermodynamic characterization of the metal-hydrogen bond in a series of cobalt-hydride complexes

A detailed structural and thermodynamic study of a series of cobalt-hydride complexes is reported. This includes structural studies of [H(2)Co(dppe)(2)](+), HCo(dppe)(2), [HCo(dppe)(2)(CH(3)CN)](+), and [Co(dppe)(2)(CH(3)CN)](2+), where dppe = bis(diphenylphosphino)ethane. Equilibrium measurements are reported for one hydride- and two proton-transfer reactions. These measurements and the determinations of various electrochemical potentials were used to determine 11 of 12 possible homolytic and heterolytic solution Co-H bond dissociation free energies of [H(2)Co(dppe)(2)](+) and its monohydride derivatives. These values provide a useful framework for understanding observed and potential reactions of these complexes. These reactions include the disproportionation of [HCo(dppe)(2)](+) to form [Co(dppe)(2)](+) and [H(2)Co(dppe)(2)](+), the reaction of [Co(dppe)(2)](+) with H(2), the protonation and deprotonation reactions of the various hydride species, and the relative ability of the hydride complexes to act as hydride donors.     

A Tetrameric Cage with D2h Symmetry through Alkyne Metathesis

Shape‐persistent covalent organic polyhedrons (COPs) with ethynylene linkers are usually prepared through kinetically controlled cross‐coupling reactions. The high‐yielding synthesis of ethynylene‐linked rigid tetrameric cages via one‐step alkyne metathesis from readily accessible triyne precursors is presented. The tetrameric cage contains two macrocyclic panels and exhibits D_2h symmetry. The assembly of such a COP is a thermodynamically controlled process, which involves the initial formation of macrocycles as key intermediates followed by the connection of two macrocycles with ethynylene linkages. With a large internal cavity, the cage exhibits a high binding selectivity toward C₇₀ (K=3.9×10³ L mol^?1) over C₆₀ (no noticeable binding).