A general and modular synthesis of monoimidouranium(IV) dihalides

The conproportionation reaction between the dimeric diimidouranium(V) species [U(N(t)Bu)(2)(I)((t)Bu(2)bpy)](2) ((t)Bu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl) and UI(3)(THF)(4) in the presence of additional (t)Bu(2)bpy yields U(N(t)Bu)(I)(2)((t)Bu(2)bpy)(THF)(2) (2), an unprecedented example of a monoimidouranium(IV) dihalide complex. The general synthesis of this family of uranium(IV) derivatives can be achieved more readily by adding 2 equiv of MN(H)R (M = Li, K; R = (t)Bu, 2,6-(i)PrC(6)H(3), 2-(t)BuC(6)H(4)) to UX(4) in the presence of coordinating Lewis bases to give complexes with the general formula U(NR)(X)(2)(L)(n) (X = Cl, I; L = (t)Bu(2)bpy, n = 1; L = THF, n = 2). The complexes were characterized by (1)H NMR spectroscopy and single-crystal X-ray diffraction analysis of compounds 2 and {U[N(2,6-(i)PrC(6)H(3))](Cl)(2)(THF)(2)}(2) (4). (The X-ray structures of 5 and 6 are reported in the Supporting Information.)     

On L-spaces and left-orderable fundamental groups

Examples suggest that there is a correspondence between L-spaces and three-manifolds whose fundamental groups cannot be left-ordered. In this paper we establish the equivalence of these conditions for several large classes of manifolds. In particular, we prove that they are equivalent for any closed, connected, orientable, geometric three-manifold that is non-hyperbolic, a family which includes all closed, connected, orientable Seifert fibred spaces. We also show that they are equivalent for the twofold branched covers of non-split alternating links. To do this we prove that the fundamental group of the twofold branched cover of an alternating link is left-orderable if and only if it is a trivial link with two or more components. We also show that this places strong restrictions on the representations of the fundamental group of an alternating knot complement with values in $\text{ Homeo}_+(S^1)$ .     

Gold-catalysed oxyarylation of styrenes and mono- and gem-disubstituted olefins facilitated by an iodine(III) oxidant

1-Hydroxy-1,2-benziodoxol-3(1H)-one (IBA) is an efficient terminal oxidant for gold-catalysed, three-component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem-disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor-based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced. In addition, the IBA-derived co-products can be recovered and recycled.     

Static and dynamic analysis of side-mode suppression of widely tunable sampled grating DBR (SG-DBR) lasers

Side-mode suppression is an important issue for widely tunable laser design and applications. In this paper, we have developed a relatively simple algorithm to analyze side-mode suppression of widely tunable sampled grating distributed Bragg reflector (SG-DBR) lasers by using the Transfer Matrix Method (TMM) in combination with multimode rate equations. The dependence of gain spectrum on wavelength is also included in this model, and its effects on tuning characteristics of the devices are investigated for the first time. Static tuning characteristics and dynamic behaviors of wavelength switching are simulated. Results agree well with the experimental results reported.     

A novel and highly stereoselective route for the synthesis of non-racemic 3-substituted isoindolin-1-one targets

A new, versatile and highly stereoselective approach for the synthesis of non-racemic 3-substituted isoindolin-1-ones is described from a readily available chiral template. The potential of this new protocol is demonstrated through the synthesis of an enantiomerically enriched 3-alkyl N-H isoindolin-1-one target with an e.e. of 98%.     

Synthesis-enabled exploration of chiral and polar multivalent quaternary sulfides

An innovative method of synthesis is reported for the large and diverse (RE)₆(TM)_x(Tt)₂S₁₄ (RE = rare-earth, TM = transition metals, Tt = Si, Ge, and Sn) family of compounds (∼1000 members, ∼325 contain Si), crystallizing in the noncentrosymmetric, chiral, and polar P6₃ space group. Traditional synthesis of such phases involves the annealing of elements or binary sulfides at elevated temperatures. The atomic mixing of refractory components technique, presented here, allows the synthesis of known members and vastly expands the family to nearly the entire transition metal block, including 3d, 4d, and 5d TMs with oxidation states ranging from 1+ to 4+. Arc-melting of the RE, TM, and tetrel elements of choice forms an atomically-mixed precursor, which readily reacts with sulfur providing bulk powders and large single crystals of the target quaternary sulfides. Detailed in situ and ex situ experiments show the mechanism of formation, which involves multiphase binary sulfide intermediates. Crystal structures and metal oxidation states were corroborated by a combination of single crystal X-ray diffraction, elemental analysis, EPR, NMR, and SQUID magnetometry. The potential of La₆(TM)_x(Tt)₂S₁₄ compounds for non-linear optical applications was also demonstrated.

Synthesis from atomically-mixed precursors opens up a phase space to hundreds of chiral and polar sulfide semiconductors with almost any transition metal in variable oxidation states.     

Frustrated Lewis Pair Mediated 1,2-Hydrocarbation of Alkynes

Frustrated Lewis pair (FLP) chemistry enables a rare example of alkyne 1,2-hydrocarbation with N-methylacridinium salts as the carbon Lewis acid. This 1,2-hydrocarbation process does not proceed through a concerted mechanism as in alkyne syn-hydroboration, or through an intramolecular 1,3-hydride migration as operates in the only other reported alkyne 1,2-hydrocarbation reaction. Instead, in this study, alkyne 1,2-hydrocarbation proceeds by a novel mechanism involving alkyne dehydrocarbation with a carbon Lewis acid based FLP to form the new C−C bond. Subsequently, intermolecular hydride transfer occurs, with the Lewis acid component of the FLP acting as a hydride shuttle that enables alkyne 1,2-hydrocarbation.     

Unexpected change in charge transfer behavior in a cobalt(II) porphyrin-fullerene conjugate that stabilizes radical ion pair states

Two cobalt(II) porphyrin-C(60) malonate-linked conjugates, the mono-connected Co1 and the bis-connected trans-2 isomer Co3, have been synthesized for the first time either by direct cyclopropanation with the precursor malonate Co4 or by metalation of the bisadduct H(2)3. For the investigation of the interaction between the porphyrin donor and fullerene acceptor within these dyads, electrochemical and photophysical investigations have been carried out. Compared to Zn3 and trans-2 bisadduct 7, the first reduction of the fullerene moiety within Co3 becomes easier (40 mV in dichloromethane and 20 mV in benzonitrile), indicating significant interactions between the pi-system of the fullerene and the d-orbitals of the central Co atom. Compared to the Co complexes 9, Co4, and Co1, the first oxidation of Co3 is considerably shifted to more positive potentials, if benzonitrile instead of dichloromethane is used as solvent. At the same time, the oxidation is no longer centered on the Co(II) center but on the porphyrin macrocycle, as corroborated by spectroelectrochemistry. A similar solvent dependence was observed in transient absorption spectroscopic measurements. In toluene, benzonitrile and anisole photoinduced electron transfer within Co3 leads to the formation of a charge-separated state Co(II)P.+ -C(60).- with a lifetime of 560 +/- 20 ns in benzonitrile, whereas in other solvents such as THF, nitrobenzene, ortho-diclorobenzene, and tert-butylbenzene the formation of a Co(III)P-C(60).- as transient was detected, which is, however, short-lived (860 +/- 40 ps in THF) and exhibits charge recombination dynamics that are in the Marcus inverted region. Particularly important is the fact that the electronic coupling (V) in Co(III)P-C(60).- is 18 cm(-1) substantially smaller than the V value of 313 cm(-1) in ZnP.+ -C(60).- .     

Facets of the <Emphasis Type="Italic">r</Emphasis>-Stable (<Emphasis Type="Italic">n</Emphasis>, <Emphasis Type="Italic">k</Emphasis>)-Hypersimplex

Let k, n, and r be positive integers with k < n and \({r \leq \lfloor \frac{n}{k} \rfloor}\). We determine the facets of the r-stable n, k-hypersimplex. As a result, it turns out that the r-stable n, k-hypersimplex has exactly 2n facets for every \({r < \lfloor \frac{n}{k} \rfloor}\). We then utilize the equations of the facets to study when the r-stable hypersimplex is Gorenstein. For every k > 0 we identify an infinite collection of Gorenstein r-stable hypersimplices, consequently expanding the collection of r-stable hypersimplices known to have unimodal Ehrhart \({\delta}\)-vectors.     

Thermally stable recyclable naphthalenediimide–siloxane polymers

We report here the synthesis and study of naphthalenediimide–siloxane polymers with high thermal stability. Two of the five polymers investigated could be developed into recyclable materials. We use solid-state ²⁹Si NMR to evaluate the degree of cross-linking and polymerisation in our materials.