N‐Annulated Perylene‐Substituted and Fused Porphyrin Dimers with Intense Near‐Infrared One‐Photon and Two‐Photon Absorption

Fusion of two N‐annulated perylene (NP) units with a fused porphyrin dimer along the S₀–S₁ electronic transition moment axis has resulted in new near‐infrared (NIR) dyes 1 a / 1 b with very intense absorption (ε>1.3×10⁵ M ^?1 cm^?1) beyond 1250 nm. Both compounds displayed moderate NIR fluorescence with fluorescence quantum yields of 4.4×10^?6 and 6.0×10^?6 for 1 a and 1 b , respectively. The NP‐substituted porphyrin dimers 2 a / 2 b have also been obtained by controlled oxidative coupling and cyclodehydrogenation, and they showed superimposed absorptions of the fused porphyrin dimer and the NP chromophore. The excited‐state dynamics of all of these compounds have been studied by femtosecond transient absorption measurements, which revealed porphyrin dimer‐like behaviour. These new chromophores also exhibited good nonlinear optical susceptibility with large two‐photon absorption cross‐sections in the NIR region due to extended π‐conjugation. Time‐dependent density functional theory calculations have been performed to aid our understanding of their electronic structures and absorption spectra.     

顶板砂岩富水性的矿井瞬变电磁法探测

介绍了矿井瞬变电磁法探测技术的原理与方法，并以山东裕隆集团唐阳煤矿631综放工作面瞬变电磁法探测为例，分析了矿井瞬变电磁法在探测工作面顶板富水性中的应用。通过井下探放水钻孔及实际揭露资料验证，该方法探测工作面顶板富水位置和范围是非常有效的物探方法之一，能为井下水害预报和防治提供可靠依据。     

Active compensation of rf-pulse transients

A new approach to compensate rf-pulse transients is proposed. Based on the idea of the response theory of a linear system, a formula is derived to obtain the required excitation voltage profile back from the intended target rf-pulse shape. The validity of the formula is experimentally confirmed by monitoring the rf-field created inside the sample coil with a pickup coil. Since this approach realizes accurate rf-pulse shapes without reducing the Q-factor of the tank circuit of the probe, it can be used not only to suppress the transient tail of the rf-pulse, but also as a general concept for accurate rf-pulsing.     

Cluster chemistry in the solid state: Structured diffuse scattering,oxide/fluoride ordering and polar behaviour in transition metal oxyfluorides

Oxide/fluoride ordering in three families of ‘disordered’ transition metal oxyfluoride compounds is carefully investigated and used to obtain insight into why the constituent inherently acentric octahedral units do not usually order in a long range ordered polar sense. Observed highly structured diffuse intensity distributions are used in each case to analyze the local crystal chemistry and orientational ordering rules governing the way in which the dipole moments from the individual polar pseudo-octahedral units add together. The common local oxide/fluoride ordering rules, the consequences of these rules for polar behaviour on the local scale as well as the role of configurational entropy and energy minimization in suppressing long range polar order are highlighted.     

Photodegradable transient bilayered poly(phthalaldehyde) with improved shelf life

Metastable poly(phthalaldehyde) (PPHA) can be triggered to depolymerize under visible light by incorporation of photosensitive compounds, such as a photoacid generator (PAG), which can generate a strong acid in situ. However, photosensitive compounds can be thermally unstable and have limited shelf life, causing inadvertent device triggering. It can also be difficult to fabricate components that are photosensitive because special lighting conditions are needed. In this paper, nonphotosensitive PPHA films were formed and made photosensitive at the point of use. This improved the material shelf life and manufacturability by adding a second, PAG‐containing layer to the original nonphotosensitive layer at an optimal point before use. The catalytic photoacid was generated rapidly by exposure of the PAG‐containing layer to radiation. Depolymerization of PPHA via the acid catalyst was followed by diffusion of the acid into the nonphotosensitive layer causing it to depolymerize. Diffusion of the photoacid into the nonphotosensitive medium was quantified at various temperatures. Photoacid diffusion in a liquid, moving‐front caused depolymerization of the nonphotosensitive PPHA layer. The fabricated bilayer structure allowed for better stability of the structural material using PPHA while still achieving transience.     

Copper-Catalyzed Enantioselective Reductive Aldol Reaction of α,β-Unsaturated Carboxylic Acids to Alkyl Aryl Ketones: Silanes as Activator and Transient Protecting Group

The first enantioselective reductive aldol reaction of unprotected α,β-unsaturated carboxylic acids was developed by employing a copper/bisphosphine catalyst. The reaction features in situ protection and activation of an α,β-unsaturated carboxylic acid by a hydrosilane. The copper enolate formed in situ reacts with an alkyl aryl ketone to afford the β-hydroxy carboxylic acid with excellent enantioselectivity (up to 99 % ee). The corresponding gram-scale reaction with a low catalyst loading and the derivatization of the β-hydroxy carboxylic acids highlight the practicality of this transformation.