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151.
Dr. Florian Rauch Peter Endres Dr. Alexandra Friedrich Dr. Daniel Sieh Dr. Martin Hähnel Dr. Ivo Krummenacher Prof. Dr. Holger Braunschweig Prof. Dr. Maik Finze Prof. Dr. Lei Ji Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(57):12951-12963
Using a new divergent approach, conjugated triarylborane dendrimers were synthesized up to the 2nd generation. The synthetic strategy consists of three steps: 1) functionalization, via iridium catalyzed C−H borylation; 2) activation, via fluorination of the generated boronate ester with K[HF2] or [N(nBu4)][HF2]; and 3) expansion, via reaction of the trifluoroborate salts with aryl Grignard reagents. The concept was also shown to be viable for a convergent approach. All but one of the conjugated borane dendrimers exhibit multiple, distinct and reversible reduction potentials, making them potentially interesting materials for applications in molecular accumulators. Based on their photophysical properties, the 1st generation dendrimers exhibit good conjugation over the whole system. However, the conjugation does not increase further upon expansion to the 2nd generation, but the molar extinction coefficients increase linearly with the number of triarylborane subunits, suggesting a potential application as photonic antennas. 相似文献
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Yvar Van Den Winkel Jeroen Van Der Laarse Frans J. J. De Kanter Thomas Van Der Does Friedrich Bickelhaupt Wilberth J. J. Smeets Anthony L. Spek 《Heteroatom Chemistry》1991,2(1):17-28
The synthesis of 2,2′-bis(bis(dimethylamino)-phosphino)-3,3′5,5′-tetra-tert-butylbiphennyl ( 5 ) is described. It was extensively studied by 1H, 13C, and 31P NMR spectroscopy. Furthermore, the X-ray analysis of 5 is reported. Crystals of 5 are tetragonal, space group P¯421c, a = b = 24.770 (3) Å, c = 12.658 (4) Å, Z = 8. The surprising reaction of 5 with proton acids leading to the formation of various phosphorus containing five- and six-membered ring compounds is discussed. On reaction of one of the six-membered ring compounds ( 9 ) with magnesium in THF, a λ3, λ5-diphosphaphenanthrene ( 19 ) was obtained. 相似文献
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Erik Geissler Anne-Marie Hecht Simon Mallam Ferenc Horkay Mikls Zrinyi 《Macromolecular Symposia》1990,40(1):101-108
Small angle neutron scattering measurements were performed on polydimethylsiloxane-toluene solutions and gels at different degrees of swelling. The scattering signal of the gel was decomposed into a solution-like part and a static part. The thermodynamic information obtained from the solution-like part of the signal is compared with macroscopic swelling pressure observations. 相似文献
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For swollen polymer networks there is no generally accepted relation between the macroscopic osmotic properties and the scattering behaviour. Detailed information on the relationship between these properties can, however, be deduced from complementary measurements of osmotic and elastic behaviour, small angle neutron and X-ray scattering (SANS and SAXS) and quasi-elastic light scattering. We describe such an investigation in two types of networks, differing in the mechanism of cross-linking. The SANS spectra yield information on the structure, which is generated both by the dynamics of the system and by long range static constraints. The former, arising from thermodynamic concentration fluctuations, governs the macroscopic osmotic and elastic moduli of the swollen network. The static superstructure in the gel reflects local variations in the cross-link density. The resulting concentration polydispersity, <δφ2>/φ2, is determined by the details of the cross-linking procedure. Its concentration dependence as a function of gel swelling can be expressed in terms of the same macroscopic osmotic and elastic variables as those that govern the thermodynamic properties of the gel. 相似文献