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101.
A detailed investigation of the influence of counterions on the [N–I–N]+ halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N–I–N]+ halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in the solid state by single crystal X-ray crystallography. Molecular systems encompassing weakly coordinating counterions behave similarly to the corresponding silver(i) centered coordination complexes. In contrast, systems possessing moderately or strongly coordinating anions show a distinctly different behavior. Such silver(i) complexes are converted into multi-coordinate geometries with strong Ag–O bonds, whereas the iodine centered systems remain linear and lack direct charge transfer interaction with the counterion, as verified by 15N NMR and DFT computation. This suggests that the [N–I–N]+ halogen bond may not be satisfactorily described in terms of a pure coordination bond typical of transition metal complexes, but as a secondary bond with a substantial charge-transfer character.  相似文献   
102.
Polynitrile anions are important in both coordination chemistry and molecular materials chemistry, and are interesting for their extensive electronic delocalization. The title compound crystallizes with two symmetry‐independent half 4,4′‐bipyridine‐1,1′‐diium (bpyH22+) cations and two symmetry‐independent 1,1,3,3‐tetracyano‐2‐ethoxypropenide (tcnoet) anions in the asymmetric unit. One of the bpyH22+ ions is located on a crystallographic twofold rotation axis (canted pyridine rings) and the other is located on a crystallographic inversion center (coplanar pyridine rings). The ethyl group of one of the tcnoet anions is disordered over two sites with equal populations. The extended structure exhibits two separate N—H...NC hydrogen‐bonding motifs, which result in a sheet structure parallel to (010), and weak C—H...NC hydrogen bonds form joined rings. Two types of multicenter CN...π interactions are observed between the bpyH22+ rings and tcnoet anions. An additonal CN...π interaction between adjacent tcnoet anions is observed. Using density functional theory, the calculated attractive energy between cation and anion pairs in the tcnoet...π(bipyridinediium) interactions were found to be 557 and 612 kJ mol−1 for coplanar and canted bpyH22+ cations, respectively.  相似文献   
103.
This review focuses on new families of spin crossover (SCO) complexes based on polynitrile anions as new anionic ligands or on polyazamacrocycles as neutral macrocyclic ligands. We have shown that the structural and electronic characteristics (original coordination modes and high electronic delocalization) of the polynitrile anions can be tuned by slight chemical modifications such as substitution of functional groups or variation of the negative charge to design new discrete or polymeric SCO systems.In our ongoing work on the design of new molecular systems based on new ligands that can be fine-tuned via chemical modifications, another promising way which has been recently developed in our group concerns the use of new neutral polydentate ligands which are able to tune the ligand field energy around the metal centre. Here we report some recent original Fe(II) SCO complexes based on such polydentate ligands.  相似文献   
104.
The use of polynitrile anions as ligands (L) either alone or in combination with neutral co-ligands (L′) is a very promising and appealing strategy to get molecular architectures with different topologies and dimensionalities thanks to their ability to coordinate and bridge metal ions in many different ways. The presence of several potentially coordinating nitrile groups (or even other donor groups as –OH, –SH or –NH2), their rigidity and their electronic delocalization allow the synthesis of original magnetic high dimensional coordination polymers with transition metals ions. Furthermore, these ligands have shown coordinating and bridging capabilities in novel discrete and polymeric bistable materials (materials showing original magnetic behaviours or spin crossover (SCO) transitions). Here we report an overview of the results obtained with some of these modified polynitrile ligands, showing their rich coordination chemistry and their crucial role in new molecular materials exhibiting unusual magnetic transitions.  相似文献   
105.
Highly efficient removal of endocrine‐disrupting compounds (EDCs) such as 17β‐estradiol (E2), 4‐nonylphenol (NP) and atrazine from water was achieved using a novel macroporous adsorption medium. The medium consisted of a macroporous poly(vinyl alcohol) (PVA) cryogel with molecularly imprinted polymer (MIP) particles embedded in it. The MIP was prepared using E2, NP and atrazine as templates. The macroporous composite molecularly imprinted cryogels were formed inside the open‐ended protective shells, known as Kaldnes carriers. These adsorbents (defined as Macroporous Gel Particles, MGPs) were evaluated on the removal of E2, NP and atrazine from water using different column configurations, namely column filled with the MGPs (packed‐bed column) and in moving‐bed reactors (defined here as moving‐bed MGPs reactor). Complete binding (> 99%) of E2 from a spiked aqueous solution (1 mg/L) was achieved using E2‐MIP/MGPs in a moving‐bed MGPs reactor at the retention time in the reactor of 4 min, while only 77% was bound to the nonimprinted medium (NIP/MGPs). Similar results were also obtained for the adsorption medium imprinted with atrazine. All contaminants studied (E2, atrazine and NP) were effectively removed from water at low (environmentally relevant) concentrations by the respective adsorption medium.  相似文献   
106.
Summary: Hydrogels were synthesized by polymerization of 2-Hydroxy ethylmethacrylate (HEMA) in the presence of ethyleneglycoldimethacrylate (EGDMA) as a crosslinking agent. Structural information and thermophysical properties of the hydrogels were analyzed using Fourier-Transform Infrared spectroscopy, thermogravimetrical analysis, and differential scanning calorimetry. The swelling behaviour of the obtained chemically crosslinked P(HEMA-EGDMA) networks in aqueous solution was investigated as a function of the pH value and concentration of crosslinking agent. Plateau values were found at equilibrium swelling for a low pH value after one day swelling, whereas increasing water uptake was obtained for pH = 6.32 even at swelling times of more than five days. For short swelling times, a linear relationship between swelling ratio and time was found. Experimental data were rationalized using Fick's second law of diffusion. For early and moderate times of diffusion, threshold values were found in all cases considered here, indicating a Fickian behaviour below and a non-Fickian diffusion mechanism above the threshold.  相似文献   
107.
We study the projective logarithmic potential Gμ of a probability measure μ on the complex projective space Pn. We prove that the range of the operator μ?Gμ is contained in the (local) domain of definition of the complex Monge–Ampère operator acting on the class of quasi-plurisubharmonic functions on Pn with respect to the Fubini–Study metric. Moreover, when the measure μ has no atom, we show that the complex Monge–Ampère measure of its logarithmic potential is an absolutely continuous measure with respect to the Fubini–Study volume form on Pn.  相似文献   
108.
Quinovic acid-3-O-alpha-L-rhamnopyranoside (1), quinovic acid-3-O-beta-D-fucopyranoside (2), quinovic acid-3-O-beta-D-glucopyranosyl (1 --> 4)-beta-D-fucopyranoside (3), methyl gallate (4) and ethyl gallate (5) were isolated from the ethyl acetate extract of Bridelia ndellensis barks by fractionation. Compounds 1-3 showed significant inhibitory activity against snake venom phosphodiesterase-I.  相似文献   
109.
Prunusins A (1) and B (2), the new C‐alkylated flavonoids, have been isolated from the seed kernels of Prunus domestica. Their structures were assigned from 1H and 13C nuclear magnetic resonating spectra, DEPT and by correlation spectroscopy, HMQC and HMBC experiments. 3, 5, 7, 4′‐Tetrahydroxyflavone (3) and 3, 5, 7‐trihydroxy‐8, 4′‐dimethoxyflavone (4) have also been reported from this species. Both compounds (1) and (2) showed significant antifungal activity against pathogenic fungus Trichophyton simmi. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   
110.
A method for high throughput screening of Green Fluorescent Proteins carrying metal binding tags in bacteria was developed. A random four amino acids tag-peptide library was successfully generated in E. coli. A 96-microtiter plate assembled with metal-iminodiacetic acid small cryogel columns was used for library screening. For the first time we were able to simultaneously screen a metal binding peptide tags library obtained from E. coli against different metal ions. From screening 25 different tags, three clones were able to bind to all metal ions studied (Ni2+, Zn2+, Co2+ and Cd2+). It was clearly demonstrated that the new construct could facilitate the screening of large peptide libraries.  相似文献   
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