Iron‐Catalyzed C(sp2)H and C(sp3)H Methylations of Amides and Anilides

The so‐called magic methyl effect significantly boosts the bioactivities and physical properties of pharmacologically active drugs. Direct introduction of the methyl group by C?H activation was accomplished with a versatile iron catalyst, which enabled the C?H methylation of (hetero)benzamides, anilides, alkenes, and even alkanes by triazole assistance in a chemo‐, site‐ and diastereo‐selective fashion.     

Condensed‐Phase,Halogen‐Bonded CF3I and C2F5I Adducts for Perfluoroalkylation Reactions

A family of practical, liquid trifluoromethylation and pentafluoroethylation reagents is described. We show how halogen bonding can be used to obtain easily handled liquid reagents from gaseous CF₃I and CF₃CF₂I. The synthetic utility of the new reagents is exemplified by a novel direct arene trifluoromethylation reaction as well as adaptations of other perfluoroalkylation reactions.     

Tetrasubstituted Peropyrenes Formed by Reductive Aromatization: Synthesis,Functionalization and Characterization

The chromophore class of 1,3,8,10-tetrasubstituted peropyrenes was effectively synthesized from peropyrenequinone via a Zn-mediated reductive aromatization approach. In one step, a symmetric functionalization of the peropyrene backbone introducing silylethers ( 2 , 3 ), pivaloyl ( 4 ), triflyl ( 5 ) and also phosphinite ( 6 ) groups was established. Furthermore, the potential of using 4 and 5 in transition metal catalysed cross couplings was explored leading to 1,3,8,10-tetraaryl ( 8 - 11 ) and tetraalkynyl ( 7 ) peropyrenes. The influence of various substituents on the optoelectronic properties of these π-system extended peropyrenes was investigated in solid state by means of X-ray crystallography, in solution by means of UV-Vis and fluorescence spectroscopy and by their redox properties studied via cyclic voltammetry. By comparison with DFT and TD-DFT calculations, it could be elucidated that introduction of a broad variety of substituents in such versatile one or two step procedures leads to peropyrenes with easily tunable HOMO and LUMO energies ranging in a gap window of 0.8 eV. The frontier molecular orbital energies identify the target molecules as promising candidates for hole transporting semiconductors.     

Synthesis and Optoelectronic Properties of a Quinoxalino-Phenanthrophenazine (QPP) Extended Tribenzotriquinacene (TBTQ)

A six-step synthesis towards a tribenzotriquinacene (TBTQ) bearing three quinoxalinophenanthrophenazine (QPP) units is presented. The optoelectronic properties are investigated and the effect of the three-dimensional arrangement of the individual QPP planes is examined using optical spectroscopy, electrochemical analysis and quantum-chemical calculations.     

Analytical and Numerical Treatment of Continuous Ageing in the Voter Model

The conventional voter model is modified so that an agent’s switching rate depends on the ‘age’ of the agent—that is, the time since the agent last switched opinion. In contrast to previous work, age is continuous in the present model. We show how the resulting individual-based system with non-Markovian dynamics and concentration-dependent rates can be handled both computationally and analytically. The thinning algorithm of Lewis and Shedler can be modified in order to provide an efficient simulation method. Analytically, we demonstrate how the asymptotic approach to an absorbing state (consensus) can be deduced. We discuss three special cases of the age-dependent switching rate: one in which the concentration of voters can be approximated by a fractional differential equation, another for which the approach to consensus is exponential in time, and a third case in which the system reaches a frozen state instead of consensus. Finally, we include the effects of a spontaneous change of opinion, i.e., we study a noisy voter model with continuous ageing. We demonstrate that this can give rise to a continuous transition between coexistence and consensus phases. We also show how the stationary probability distribution can be approximated, despite the fact that the system cannot be described by a conventional master equation.     

Broadband Multidimensional Spectroscopy Identifies the Amide II Vibrations in Silkworm Films

We used two-dimensional infrared spectroscopy to disentangle the broad infrared band in the amide II vibrational regions of Bombyx mori native silk films, identifying the single amide II modes and correlating them to specific secondary structure. Amide I and amide II modes have a strong vibrational coupling, which manifests as cross-peaks in 2D infrared spectra with frequencies determined by both the amide I and amide II frequencies of the same secondary structure. By cross referencing with well-known amide I assignments, we determined that the amide II (N-H) absorbs at around 1552 and at 1530 cm^–1 for helical and β-sheet structures, respectively. We also observed a peak at 1517 cm⁻¹ that could not be easily assigned to an amide II mode, and instead we tentatively assigned it to a Tyrosine sidechain. These results stand in contrast with previous findings from linear infrared spectroscopy, highlighting the ability of multidimensional spectroscopy for untangling convoluted spectra, and suggesting the need for caution when assigning silk amide II spectra.     

Alkene insertion reactivity of a o-carboranyl-substituted 9-borafluorene

The synthesis of 9-borafluorene with an electron-withdrawing o-carboranyl substituent and its reactions with a series of alkenes are described. The o-carboranyl substituent is bonded via one of the cluster carbon atoms to the boron atom of the 9-borafluorene moiety. In all cases, the reactions afford partly saturated analogs of borepins (i.e. 6,7-dihydroborepins) by unprecedented alkene insertion into the endocyclic B–C bond of the borole ring. Comparative studies with 9-bromo-9-borafluorene illustrate the superior insertion reactivity of the carboranyl-substituted derivative. A suite of experimental and computational techniques disclose the unique properties of the 9-borafluorene and provide insight into how the 9-carboranyl substituent affects its chemical reactivity.

A 9-carboranyl-substituted 9-borafluorene is reported, which is capable of undergoing efficient ring expansion to 6,7-dihydroborepins by a previously unknown alkene insertion.     

Unidirectional mechanical amplification as a design principle for an active microphone

Amplification underlies the operation of many biological and engineering systems. Simple electrical, optical, and mechanical amplifiers are reciprocal: the backward coupling of the output to the input equals the forward coupling of the input to the output. Unidirectional amplifiers that occur often in electrical and optical systems are special nonreciprocal devices in which the output does not couple back to the input even though the forward coupling persists. Here we propose a scheme for unidirectional mechanical amplification that we utilize to construct an active microphone. We show that amplification improves the microphone's threshold for detecting weak signals and that unidirectionality prevents distortion.