Visible‐Light‐Triggered Molecular Photoswitch Based on Reversible E/Z Isomerization of a 1,2‐Dicyanoethene Derivative

A designed bis(dithienyl) dicyanoethene‐based, strictly E/Z photoswitch (4TCE) operates through state‐selective (E and Z isomer) photoactivation with visible light. The E and Z isomers of 4TCE exhibit remarkably different spectroscopic characteristics, including a large separation (70 nm) in their absorption maxima (λ_max) and a 2.5‐fold increase in molar extinction coefficient from cis to trans. The energetically stable trans form can be completely converted to the cis form within minutes when exposed to white light, whereas the reverse isomerization occurs readily upon irradiation by blue light (λ<480 nm) or completely by thermal conversion at elevated temperatures. These features together with excellent thermal stability and photostability of both isomers make this new E/Z photoswitch a promising building block for photoswitchable materials that operate without the need for UV light.     

Photoinduced Charge‐Carrier Generation in Epitaxial MOF Thin Films: High Efficiency as a Result of an Indirect Electronic Band Gap?

For inorganic semiconductors crystalline order leads to a band structure which gives rise to drastic differences to the disordered material. An example is the presence of an indirect band gap. For organic semiconductors such effects are typically not considered, since the bands are normally flat, and the band‐gap therefore is direct. Herein we show results from electronic structure calculations demonstrating that ordered arrays of porphyrins reveal a small dispersion of occupied and unoccupied bands leading to the formation of a small indirect band gap. We demonstrate herein that such ordered structures can be fabricated by liquid‐phase epitaxy and that the corresponding crystalline organic semiconductors exhibit superior photophysical properties, including large charge‐carrier mobility and an unusually large charge‐carrier generation efficiency. We have fabricated a prototype organic photovoltaic device based on this novel material exhibiting a remarkable efficiency.     

Comparing historical and contemporary opera singers with historical and contemporary Jewish cantors

This study is an attempt to ascertain if singers from different traditions and milieus follow similar aesthetic trends regardless of training and/or background. Cantors who sang the Jewish synagogue liturgy during the Golden Age of cantorial singing prior to World War II came from Eastern and Central Europe. For the most part, they were not trained in the classical Western opera tradition. They received training from choir leaders and other cantors and the training was primarily in the modes of synagogue chant. Cantors today receive the same kinds of training that opera singers receive, often from the same teachers. Four groups of singers, consisting of four singers in each group, were utilized in this study. The four groups are: historical opera singers, contemporary opera singers, historical cantors, and contemporary cantors. The historical opera singer recordings date from as early as 1909 to as late as 1939. It was not possible to determine the dates of the historical cantor recordings. However, the four cantors chosen for this group were active only to the 1940s. Contemporary samples were taken from CDs and/or live recordings and all the singers from the contemporary groups are either still active or were active in the 1960s through the 1980s and all of them are considered to be premier-level singers in their respective areas. The variables analyzed were: vibrato pulse rate, frequency variation of the vibrato pulse above and below the mean sustained sung frequency in percent, the mean amplitude variation of the amplitude vibrato pulse above and below the mean sustained amplitude in percent and the fast Fourier transform (FFT) power spectrum of the sustained samples. Results indicate that most of the significant differences were found between eras and not between groups within a time period.     

Location of superconductivity in La2-βSrβCuO4

Evidence is presented that the superconductivity of La_{2 ?β} Sr_β CuO₄ and La₂CuO4_+δ occurs via holes in the LaO planes, rather than in the CuO₂ planes.     

When linear and weak discrepancy are equal

The linear discrepancy of a poset P is the least k such that there is a linear extension L of P such that if x and y are incomparable, then |h_L(x)−h_L(y)|≤k, whereas the weak discrepancy is the least k such that there is a weak extension W of P such that if x and y are incomparable, then |h_W(x)−h_W(y)|≤k. This paper resolves a question of Tanenbaum, Trenk, and Fishburn on characterizing when the weak and linear discrepancy of a poset are equal. Although it is shown that determining whether a poset has equal weak and linear discrepancy is -complete, this paper provides a complete characterization of the minimal posets with equal weak and linear discrepancy. Further, these minimal posets can be completely described as a family of interval orders.     

Dichotomy for the Hausdorff dimension of the set of nonergodic directions

Given an irrational 0<λ<1, we consider billiards in the table P _λ formed by a \(\tfrac{1}{2}\times1\) rectangle with a horizontal barrier of length \(\frac{1-\lambda}{2}\) with one end touching at the midpoint of a vertical side. Let NE?(P _λ ) be the set of θ such that the flow on P _λ in direction θ is not ergodic. We show that the Hausdorff dimension of NE?(P _λ ) can only take on the values 0 and \(\tfrac{1}{2}\), depending on the summability of the series \(\sum_{k}\frac{\log\log q_{k+1}}{q_{k}}\) where {q _k } is the sequence of denominators of the continued fraction expansion of λ. More specifically, we prove that the Hausdorff dimension is \(\frac{1}{2}\) if this series converges, and 0 otherwise. This extends earlier results of Boshernitzan and Cheung.     

Synthesis of unsaturated seven-membered ring lactams through palladium-catalyzed amination and intramolecular cyclocarbonylation reactions of amines and Baylis-Hillman acetates

A versatile synthesis of unsaturated seven-membered ring lactams has been developed. The sequence involves hydroamination of Baylis-Hillman acetate with amines, followed by intramolecular cyclocarbonylation reactions of the resulting allylamines. This process can tolerate a wide array of functional groups, and affords lactams in excellent yields.     

Palladium-catalyzed domino C-S coupling/carbonylation reactions: an efficient synthesis of 2-carbonylbenzo[b]thiophene derivatives

A facile and selective palladium-catalyzed domino procedure has been developed for the preparation of 2-carbonylbenzo[b]thiophene derivatives from 2-gem-dihalovinylthiophenols. This protocol involves intramolecular C-S coupling/intermolecular carbonylation cascade sequences and allows access to various highly functionalized benzo[b]thiophenes in moderate yields.     

Degree bounds for type-A weight rings and Gelfand–Tsetlin semigroups

A weight ring in type A is the coordinate ring of the GIT quotient of the variety of flags in ℂ ⁿ modulo a twisted action of the maximal torus in SL(n,ℂ). We show that any weight ring in type A is generated by elements of degree strictly less than the Krull dimension, which is at worst O(n ²). On the other hand, we show that the associated semigroup of Gelfand–Tsetlin patterns can have an essential generator of degree exponential in n.     

Copper(I) thiocyanate-amine networks: synthesis, structure, and luminescence behavior

A series of metal-organic networks of CuSCN were prepared by direct reactions with substituted pyridine and aliphatic amine ligands, L. Thiocyanate bridging is seen in all but 1 of 11 new X-ray structures. Structures are reported for (CuSCN)L sheets (L = 3-chloro- and 3-bromopyridine, N-methylmorpholine), ladders (L = 2-ethylpyridine, N-methylpiperidine), and chains (L = 2,4,6-collidine). X-ray structures of (CuSCN)L(2) are chains (L = 4-ethyl- and 4-t-butylpyridine, piperidine, and morpholine). A unique N-thiocyanato monomer structure, (CuSCN)(3-ethylpyridine)(3), is also reported. In most cases, amine ligands are thermally released at temperatures <100 °C. Strong yellow-to-green luminescence at ambient temperature is observed for the substituted pyridine complexes. High solid state quantum efficiencies are seen for many of the CuSCN-L complexes. Microsecond phosphorescence lifetimes seen for CuSCN-L are in direct contrast to the nanosecond-lifetime emission of CuSCN. MLCT associated with pyridine π* orbitals is proposed as the excitation mechanism.