聚苯撑的合成、性能及其应用

对直链型、树枝形聚苯撑的合成、性能及其应用作了介绍，并着重描述了聚苯撑的应用。     

Synthesis,Structure, and Optical Properties of Terminally Sulfur‐Functionalized Core‐Substituted Naphthalene‐Bisimide Dyes

The synthesis, characterization, and optical properties of a series of new 2,6‐disubstituted naphthalene‐bisimide dyes as molecular rods comprising terminal AcS groups is reported. The first series of dyes ( 1 – 3 ), comprising phenylhetero (Ph‐X) core substituents, cover a broad range of the VIS spectrum, ranging from yellow ( 2 ) over red ( 3 ) to blue ( 1 ). The second series of dyes contains benzylhetero (Bn‐X) core substituents ( 4 – 7 ). For the same heteroatom connecting the substituent to the naphthalene core, both series were found to display comparable colors. For the second series, the colors were blue ( 4 ), red ( 5 ), and violet ( 6, 7 ). The Ph‐X‐substituted dyes 1 – 3 are nonfluorescent, in contrast to the Bn‐X‐substituted compounds 4 – 7 . This rich variety of optical features that can be adjusted by rather small alterations of the core substituents makes these structurally very comparable molecular rods ideal candidates for optically triggered molecular‐transport investigations. Also, thanks to the terminal AcS groups, these compounds can be placed between nobel‐metal electrodes for optically triggered transport experiments.     

The Search for Highly Colored Organic Compounds

Until now the study of organic compounds in which the π-electron system is excited by absorbed light has been mainly concentrated on the ultraviolet and visible regions of the electromagnetic spectrum. Various new applications, such as the use of conjugated organic compounds as dye lasers or as materitals for storing information with the help of diode lasers, led to the synthesis of new compounds which absorb light in the near in infrared (NIR). It is possible to use structure-color relationships to predict the properties of such new compounds when they belong to dyestuff classes which have already been studied in detail; in this case the approach involves decreasing the energy difference between the ground state and the first excited state. A less conventional starting point is provided by molecular structures in which from the outset there is only a very small energy difference between the lowest-energy electronic states; such diradicaloid molecules occupy a special position among the various types of organic compounds. It is possible by means of suitable structural modification to stabilize such molecules in a singlet from which absorbs light at very long wavelengths (i.e. at small wave numbers).     

Anionic Conduction in Blends of Poly(Pyridinium Ethyl Methacrylate Perchloride) and Poly[Oligo(Oxyethylene) Methacrylate-Co-Acrylamide]

Abstract

Blends of poly(pyridinium ethyl methacrylate perchloride) and poly[oligo(oxyethylene) methacrylate-co-acrylamide] were prepared, and the ionic conductivity and mobility of the blends were investigated. Results indicate that both the transference of perchlorate anion and the dissociation of the polymeric salt in the comblike polyether obey the thermoactivation mechanism, and that the perchlorate anion in the blends is free.     

How does the skin sense sun light? An integrative view of light sensing molecules

The consensus on the effects of excessive sun exposure on human health has long emphasized the negative effects of solar UV radiation. Nevertheless, although UV radiation has been demonized, less is known about the consequences of sun exposure while using sunscreen, which can lead to high visible light exposure. UV and visible light play key roles in vitamin D synthesis, reduction of blood pressure, among other beneficial effects. In this review, we aim to provide a comprehensive view of the wide range of responses of the human skin to sunlight by revisiting data on the beneficial and harmful effects of UV and visible light. We start by exploring the interaction of photons in the skin at several levels including physical (depth of photon penetration), chemical (light absorption and subsequent photochemical events), and biological (how cells and tissues respond). Skin responses to sun exposure can only be comprehensively understood through a consideration of the light-absorbing molecules present in the skin, especially the light-sensing proteins called opsins. Indeed, many of the cellular responses to sun exposure are modulated by opsins, which act as the “eyes of the skin”.     

Strong Electronic Communication in Linearly Elongated Rylenes Featuring Tunable Bridges

A modified synthetic pathway towards perylene-perylene dimers and a facile purification method to obtain the regioisomerically pure syn- and anti-isomers are reported. In addition, a novel perylene-naphthalene heterodimer with 30 conjugated π-electron pairs was designed and synthesized on the basis of a previously described precursor and the resulting regioisomers were separated from each other. Thereby, the opto-electronic properties of the linearly elongated chromophores could be investigated regarding the differences in length of their aromatic system and the configuration of the isomers. Further tuning of their energy gaps was realized via protonation and methylation of the dibenzimidazole-bridging unit. Extraordinary red-shifts of the absorption maxima of 62 nm for the methylated and 92 nm for the protonated perylene-perylene anti-isomer could be achieved. Moreover, the maxima for the syn-isomer could be shifted bathochromically by 87 and 113 nm, respectively.     

A Twisted Bay‐Substituted Quaterrylene Phosphorescing in the NIR Spectral Region

The preparation of the first soluble quaterrylene derivative featuring peripheral tert‐butyl substituents and sterically hindering, core‐anchored triflate groups has been achieved. This involves a facile synthetic route based on an oxidative coupling of perylene precursors in the presence of H₂O₂ as oxidant. The steric hindrance between the TfO substituents at the central bay position of the quaterrylene board triggers a strong deformation of the central perylene planarity, which forces the quaterrylene platform to adopt a twisted geometry as shown by X‐ray analysis. Exceptionally, photophysical investigations show that the core‐twisted quaterrylene phosphoresces in the NIR spectral region at 1716 nm. Moreover, third‐order nonlinear optical measurements on solutions and thin film containing the relevant molecule showed very large second hyperpolarizability values, as predicted by theoretical calculations at the CAM ‐B3LYP /6‐31G** level of theory, making this material very appealing for photonic applications.     

Inducing anti-Conformers of Biliverdin Chromophores by Reducing Sterical Hindrance

Summary. Two different types of conformational changes of the biliverdin chromophore were accomplished by the concept of reducing sterical hindrance. On one hand, model compounds unsubstituted at position 7 and/or 13 adopt the semi-extended geometry with anti-conformation of the dipyrrinone moiety. On the other hand, stretching of the chromophore with anti-conformation of the dipyrrin substructure was achieved with a model compound unsubstituted at position 12. Both kinds of anti-conformations have been proved by 2D NMR and UV-Vis spectroscopy.Current address: Voestalpine Stahl GmbH, Voest-Alpine-Straße 1, A-4020 Linz, Austria     

Synthesis of unsymmetrical 2-(2-vinyl-4H-chromen-4-ylidene)malononitrile dyes via Knoevenagel reaction

A series of new chromophores based on 4-(dicyanomethylene)-2-vinyl 4H-chromenes was synthesized and their physical properties (UV–Vis, NMR, mass spectrometry) were studied. The chromophores show moderate or good solubility in organic solvents. Solvatochromism was investigated for compounds in solvents of low (1.4-dioxane, chlorobenzene, methylene chloride) and high polarity (acetone, acetonitrile). The calculations of the first hyperpolarizability (β) was performed using M052X/6-31+G(d) approximation. Chromophore’s molecules are characterized by high calculated values of the first hyperpolarizability (β) that is only 15% lower than that of FTC analogs.     

Conjugation and cyclization—two strong driving forces leading to the formation of new chromophores

Novel chromophores formed in the solvent reactions of α-amino acids and small peptides were identified by crystal structure analysis and characterized by UV absorption. The formation of these chromophores in basic solutions was attributed to two strong driving forces—conjugation and cyclization. The discussion of possible reaction pathways could benefit the future design of α-amino acid-based chromophores.