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991.
Organic Crystals with Near‐Infrared Amplified Spontaneous Emissions Based on 2′‐Hydroxychalcone Derivatives: Subtle Structure Modification but Great Property Change 下载免费PDF全文
Xiao Cheng Kai Wang Shuo Huang Dr. Houyu Zhang Prof. Dr. Hongyu Zhang Prof. Dr. Yue Wang 《Angewandte Chemie (International ed. in English)》2015,54(29):8369-8373
A series of highly efficient deep red to near‐infrared (NIR) emissive organic crystals 1 – 3 based on the structurally simple 2′‐hydroxychalcone derivatives were synthesized through a simple one‐step condensation reaction. Crystal 1 displays the highest quantum yield (Φf) of 0.32 among the reported organic single crystals with an emission maximum (λem) over 710 nm. Comparison between the bright emissive crystals 1 – 3 and the nearly nonluminous compounds 4 – 7 clearly gives evidence that a subtle structure modification can arouse great property changes, which is instructive in designing new high‐efficiency organic luminescent materials. Notably, crystals 1 – 3 exhibit amplified spontaneous emissions (ASE) with extremely low thresholds. Thus, organic deep red to NIR emissive crystals with very high Φf have been obtained and are found to display the first example of NIR fluorescent crystal ASE. 相似文献
992.
Qing He Dr. Yu‐Fei Ao Prof. Zhi‐Tang Huang Prof. De‐Xian Wang 《Angewandte Chemie (International ed. in English)》2015,54(40):11785-11790
Anion–π interactions have been widely studied as new noncovalent driving forces in supramolecular chemistry. However, self‐assembly induced by anion–π interactions is still largely unexplored. Herein we report the formation of supramolecular amphiphiles through anion–π interactions, and the subsequent formation of self‐assembled vesicles in water. With the π receptor 1 as the host and anionic amphiphiles, such as sodium dodecylsulfate (SDS), sodium laurate (SLA), and sodium methyl dodecylphosphonate (SDP), as guests, the sequential formation of host–guest supramolecular amphiphiles and self‐assembled vesicles was demonstrated by SEM, TEM, DLS, and XRD techniques. The intrinsic anion–π interactions between 1 and the anionic amphiphiles were confirmed by crystal diffraction, HRMS analysis, and DFT calculations. Furthermore, the controlled disassembly of the vesicles was promoted by competing anions, such as NO3?, Cl?, and Br?, or by changing the pH value of the medium. 相似文献
993.
994.
Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems 下载免费PDF全文
Dawei Zhang Dr. Bastien Chatelet Eloisa Serrano Dr. Olivier Perraud Dr. Jean‐Pierre Dutasta Prof. Dr. Vincent Robert Prof. Dr. Alexandre Martinez 《Chemphyschem》2015,16(14):2931-2935
The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions. 相似文献
995.
Prof. Dr. Yasutomo Segawa Takehisa Maekawa Prof. Dr. Kenichiro Itami 《Angewandte Chemie (International ed. in English)》2015,54(1):66-81
Activation of aromatic C? H bonds by a transition metal catalyst has received significant attention in the synthetic chemistry community. In recent years, rapid and site‐selective extension of π‐electron systems by C–H activation has emerged as an ideal methodology for preparing organic materials with extended π‐systems. This Review focuses on recently reported π‐extending C–H activation reactions directed toward new optoelectronic conjugated materials. 相似文献
996.
The interactions between atoms of noble gases and π systems are generally considered as van der Waals interaction, which have not attracted attention yet. Herein, we present high‐level ab initio calculations to show the unexpected noncovalent interaction between a covalently bonded noble gas atom and a delocalized aromatic π electron using XeO3?benzene as the prototype. The CCSD(T)/CBS reference data show its strength amounting to ?10.2 kcal mol?1, comparable to a typical H‐bond or an anion–π interaction. The energy decomposition analysis reveals that the aerogen–π interaction is favored by the electrostatic interaction (27.7 %), the induction (13.4 %), and the dispersion (21.6 %). This interaction may prompt us to consider the noncovalent chemistry of aerogen derivatives in the near future. 相似文献
997.
Dr. Desmond MacLeod Carey Dr. Tatiana Gomez Dr. Cesar Morales-Verdejo Dr. Alvaro Muñoz-Castro 《ChemistryOpen》2015,4(5):651-655
The complexation of metal cations into a host–guest situation is particularly well exemplified by [2.2.2]paracyclophane and AgI, which leads to a strong cation–π interaction with a specific face of the host molecule. Through this study we sought a deeper understanding of the effects the metal center has on the NMR spectroscopic properties of the prototypical organic host, generating theoretical reasons for the observed experimental results with an aim to determine the role of the cation–π interaction in a host–guest scenario. From an analysis of certain components of the induced magnetic field and the 13C NMR shielding tensor under its own principal axis system (PAS), the local and overall magnetic behavior can be clearly described. Interestingly, the magnetic response of such a complex exhibits a large axis-dependent behavior, which leads to an overall shielding effect for the coordinating carbon atoms and a deshielding effect for the respective uncoordinated counterparts, evidence that complements previous experimental results. This proposed approach can be useful to gain further insight into the local and overall variation of NMR shifts for host–guest pairs involving both inorganic and organic hosts. 相似文献
998.
Manuel M. Bentlohner Wilhelm Klein Zohreh H. Fard Laura‐Alice Jantke Thomas F. Fssler 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(12):3819-3824
The accessibility of triads with deltahedral Zintl clusters in analogy to fullerene–linker–fullerene triads is another example for the close relationship between fullerenes and Zintl clusters. The compound {[K(2.2.2‐crypt)]4[RGe9‐CHCH CHCH‐Ge9R]}(toluene)2 (R=(2Z,4E)‐7‐amino‐5‐aza‐hepta‐2,4‐dien‐2‐yl), containing two deltahedral [Ge9] clusters linked by a conjugated (1Z,3Z)‐buta‐1,3‐dien‐1,4‐diyl bridge, was synthesized through the reaction of 1,4‐bis(trimethylsilyl)butadiyne with K4Ge9 in ethylenediamine and crystallized after the addition of 2.2.2‐cryptand and toluene. The compound was characterized by single‐crystal structure analysis as well asNMR and IR spectroscopy. 相似文献
999.
1000.
Aromatic Interactions in Organocatalyst Design: Augmenting Selectivity Reversal in Iminium Ion Activation 下载免费PDF全文
Dr. Constantin Daniliuc Dr. W. Bernd Schweizer Prof. Dr. Ryan Gilmour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(28):10031-10038
Substituting N‐methylpyrrole for N‐methyindole in secondary‐amine‐catalysed Friedel–Crafts reactions leads to a curious erosion of enantioselectivity. In extreme cases, this substrate dependence can lead to an inversion in the sense of enantioinduction. Indeed, these closely similar transformations require two structurally distinct catalysts to obtain comparable selectivities. Herein a focussed molecular editing study is disclosed to illuminate the structural features responsible for this disparity, and thus identify lead catalyst structures to further exploit this selectivity reversal. Key to effective catalyst re‐engineering was delineating the non‐covalent interactions that manifest themselves in conformation. Herein we disclose preliminary validation that intermolecular aromatic (CH–π and cation–π) interactions between the incipient iminium cation and the indole ring system is key to rationalising selectivity reversal. This is absent in the N‐methylpyrrole alkylation, thus forming the basis of two competing enantio‐induction pathways. A simple L ‐valine catalyst has been developed that significantly augments this interaction. 相似文献