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891.
A series of main‐chain metallopolymers ( P1–P10 ) was prepared by the self‐assembly of rigid‐linear π‐conjugated bis(terpyridine) monomers ( 1–10 ) with ZnII ions and was fully characterized. The polymerization was additionally confirmed by UV/vis titration experiments. A strong increase in viscosities (around 1.6 times) relative to those of the monomer solutions was found. The thermal stability of P1–P10 compared with that of 1–10 was enhanced as a result of the metallopolymerization. The electro‐optical properties of the materials were investigated in detail. Tuning of the electrochemical and photophysical properties was enabled; thus, bright purple to green photoluminescent (PL) emission (PL quantum yields of 0.12–0.81) for P1–P10 was observed in solution with the emission color strongly depending on the nature of the π‐conjugated bis(terpyridine) system. Thin homogeneous films of P6 were prepared by solution processing, that is, spin‐coating and inkjet‐printing, and exhibited intense yellow PL emission in the solid state. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4083–4098, 2009  相似文献   
892.
893.
Herein, we study the conjugation properties of three different thienoacenes, each of which has three or four fused thiophene rings, by means of Fourier transform Raman spectroscopy. The B3LYP/6-31G** vibrational analysis of all of the collected spectroscopic data evidences that the selective enhancement of a limited number of Raman scatterings is related to the occurrence in the three thienoacenes of a vibronic coupling between the lowest unoccupied frontier molecular orbital (LUMO) and some Raman-active skeletal nu(C==C) stretching modes of 1600-1300 cm(-1).  相似文献   
894.
Mark Kac's theorem on the mean recurrence time in a stationary stochastic process in discrete time with discrete states is taken as the starting point for a series of variations, most of which are formulated in terms of 0013;1 processes. Whereas the original theorem deals with the mean recurrence time of a given state under the condition that the state is realized at time 0, this condition is dropped in part of the variations; two others refer to the variance of the recurrence time and two to the Poincaré cycle of a dynamical system. Most variations consist in inequalities and formal identities for the mean first-arrival time and subsequent recurrence times for the given state.  相似文献   
895.
Herein we report the organoplatinum‐mediated bottom‐up synthesis, characterization, and properties of a novel large π‐extended carbon nanoring based on a nanographene hexa‐peri ‐hexabenzocoronene (HBC) building unit. This tubular structure can be considered as an example of the longitudinal extension of the cycloparaphenylene scaffold to form a large π‐extended carbon nanotube (CNT) segment. The cyclic tetramer of a tetramesityl HBC ([4]CHBC) was synthesized by the reaction of a 2,11‐diborylated hexa‐peri ‐hexabenzocoronene with a platinum complex, followed by reductive elimination. The structure of this tubular molecule was further confirmed by physical characterization. Theoretical calculations indicate that the strain energy of this nanoring is as high as 49.18 kcal mol−1. The selective supramolecular host–guest interaction between [4]CHBC and C70 was also investigated.  相似文献   
896.
Pentalenes represent highly reactive Hückel antiaromatics with 8π electrons. Usually, pentalenes are stabilized by incorporation of two benzene rings in a fused fashion. In dibenzo[a ,e ]pentalenes, however, the high aromaticity of the fused benzene rings compromises the inherent antiaromaticity of the pentalene core. Herein, we disclose that this forfeited antiaromaticity can be restored by fusing four additional aromatic rings onto the peripheral positions of dibenzo[a,e]pentalenes. Such polycyclic pentalenes were prepared by successive transannular cyclizations via in situ‐generated tetrakisdehydro[16]annulenes. The thus obtained compounds showed intriguing properties, for example, characteristic absorptions in the visible‐to‐near‐infrared (NIR) region and low reduction potentials. These results hence afford a design principle to produce highly antiaromatic yet stable pentalenes. The antiaromaticity of the pentalene core can be widely tuned via the degree of aromaticity of the peripherally fused rings.  相似文献   
897.
A near‐infrared (NIR) polymethine dye ( 1 ), consisting of a cyclohepta[1,2‐b ;4,3‐b′ ]dithiophene and two phenol moieties, was synthesized. This dye exhibited pH‐responsive changes in its photophysical properties due to a two‐step acid–base equilibrium that produced a protonated cation ( 1H+ ) and an anion ( 1 ). While 1H+ showed an intense fluorescence in the red region of the visible spectrum, 1 exhibited a strong absorption in the NIR region. The tropylium ion character in 1H+ induces high pK a1 and pK a2 values for 1 . Moreover, a stable radical ( 1. ) was prepared, which showed a NIR absorption band with a maximum at circa 1600 nm. The cyclic voltammogram of 1. revealed a two‐step reversible redox process that produced 1 and the cation 1+ , which is different from 1H+ . These redox processes accompany drastic electrochromic changes in the vis–NIR region. Overall, 1 is susceptible to multiple interconversions between five forms, due to the multifaceted character of the cycloheptadithiophene skeleton.  相似文献   
898.
Protein structure and function is dependent on myriad noncovalent interactions. Direct detection and characterization of these weak interactions in large biomolecules, such as proteins, is experimentally challenging. Herein, we report the first observation and measurement of long‐range “through‐space” scalar couplings between methyl and backbone carbonyl groups in proteins. These J couplings are indicative of the presence of noncovalent C−H⋅⋅⋅π hydrogen‐bond‐like interactions involving the amide π network. Experimentally detected scalar couplings were corroborated by a natural bond orbital analysis, which revealed the orbital nature of the interaction and the origins of the through‐space J couplings. The experimental observation of this type of CH⋅⋅⋅π interaction adds a new dimension to the study of protein structure, function, and dynamics by NMR spectroscopy.  相似文献   
899.
π‐Conjugated molecular cages are very challenging targets in structural organic chemistry, supramolecular chemistry, and materials science. The synthesis and physical characterizations are reported of the first three‐dimensionally π‐conjugated diradical molecular cage PTM‐C, in which two polychlorotriphenylmethyl (PTM) radicals are linked by three bis(3,6‐carbazolyl) bridges. This cage compound was synthesized mainly by intermolecular Yamamoto coupling followed by deprotonation and oxidation. It is stable and its structure was confirmed by X‐ray crystallographic analysis. The two carbon‐centered PTM radicals are weakly coupled through electronic interactions with the carbazole spacers, as revealed by optical, electronic, and magnetic measurements as well as theoretical calculations.  相似文献   
900.
We report DFT studies on some perylene‐based dyes for their electron transfer properties in solar cell applications. The study involves modeling of different donor‐π‐acceptor type sensitizers, with perylene as the donor, furan/pyrrole/thiophene as the π‐bridge and cyanoacrylic group as the acceptor. The effect of different π‐bridges and various substituents on the perylene donor was evaluated in terms of opto‐electronic and photovoltaic parameters such as HOMO‐LUMO energy gap, λmax, light harvesting efficiency(LHE), electron injection efficiency (Øinject), excited state dye potential (Edye*), reorganization energy(λ), and free energy of dye regeneration (00207608:media:qua25332:qua25332-math-0001" class="section_image" src="//wol-prod-cdn.literatumonline.com/cms/attachment/31d47cff-97a5-4d7f-bce5-529941b833a1/qua25332-math-0001.png">). The effect of various substituents on the dye–I2 interaction and hence recombination process was also evaluated. We found that the furan‐based dimethylamine derivative exhibits a better balance of the various optical and photovoltaic properties. Finally, we evaluated the overall opto‐electronic and transport parameters of the TiO2‐dye assembly after anchoring the dyes on the model TiO2 cluster assembly.  相似文献   
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