Spelling suggestions: "subject:"pseudocapacitance"" "subject:"cryptand""
1 |
Quantification of Supramolecular Complexes Involving Charged Species in Non-Aqueous Solvents: Theory and ApplicationJones, Jason William 28 May 2004 (has links)
We report for the first time a broad equilibrium model describing the complexation of ionic species in non-aqueous media that explicitly includes ion pairing for one of the components and that relies upon activities rather than molar concentrations. This model directly contradicts existing commonplace equilibrium treatments, which were shown to be incomplete, often invalid, and misleading. Experimental validation of our model was achieved through studies of pseudorotaxane formation between dibenzylammonium salts (DBAm-X) and dibenzo-24-crown-8 (DB24C8) in CDCl3:CD3CN (3:2). In that particular case, we showed that fluctuations in the apparent Ka,exp values as usually reported are attributable to ion pairing, with a dissociation constant Kipd, and that the constant Kassoc for pseudorotaxane complexation is independent of the counterion, a result of the complex existing in solution as a free cation. In accord with this model, we further described a straightforward and simple method to increase the extent of complexation by using either a ditopic cation and anion host, or adding to the charged host/guest solution a molecularly separate host capable of complexing the dissociated counterion. Also in accord with this model, we investigated the influence of the solvent¡¯s dielectric constant on Kipd and Kassoc. On the basis of competing condensation reactions between amines and ketones which were shown to occur within the timescale of host/guest recognition, we also challenged the commonly employed use of acetone in similar complexation studies involving 2o ammonium ions.
Because a major goal of this work was to ultimately increase binding efficiency and selectivity, we explored new methods to drive complexation in related pseudorotaxane systems. We noted that addition of di- or tri-topic hydrogen bond accepting anions to solutions of bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10 or bis(5-carboxy-1,3-phenylene)-32-crown-10 and paraquat di(hexafluorophosphate) served to significantly enhance host/guest interaction. The addition of Et4N+TFA- to an acetone solution of diacid crown and paraquat 2PF6 effectively boosted Ka,exp 40-fold, as estimated by 1H NMR studies. Similar increases in the apparent Ka,exp were observed upon the addition of n-Bu4N+OTs-. Evidenced by crystal structures, the increase in association resulted from chelation of the OH moieties of the crown by the di- or tri-topic anions, forming supramolecular bicyclic macrocycles (pseudocryptands) and stabilizing the complex in a cooperative manner. Significantly, Ka,exp of one of the pseudocryptands was shown to equal that determined in the corresponding cryptand complex. / Ph. D.
|
2 |
Host-Guest Systems Based on Crown Ether, Cryptand, and Pseudocryptand Hosts with Paraquat, Diquat, Secondary Ammonium, and Monopyridinium Salt GuestsHuang, Feihe 25 March 2005 (has links)
Supramolecular host-guest chemistry is a topic of great current interest. However, the further development of host-guest chemistry is still limited by the number of available host-guest recognition motifs. This makes it necessary and valuable to find new host-guest recognition motifs and apply known host-guest recognition motifs in the preparation of novel supramolecular systems.
By comparing the crystal structures of the host and its taco complex, we proved that folding is a necessary step during the formation of taco complexes. Based on the known bis(m-phenylene)-32-crown-10/paraquat recognition motif, the first solid-state supramolecular poly(taco complex) was prepared.
We demonstrate not only that bis(m-phenylene)-32-crown-10-based cryptands are powerful hosts for paraquat derivatives compared with the simple crown ether, but also that cooperative complexation can be obtained with the cryptand structure. It was shown that the significant improvement in complexation was the result of the combination of the preorganization of the cryptand hosts and the introduction of additional and optimized binding sites. Furthermore, it was demonstrated that improved complexation of bis(secondary ammonium) and bisparaquat salts could also be achieved by the formation of the pseudocryptand structure. We also prepared two dimers of inclusion cryptand/paraquat complexes driven by dipole-dipole and face-to-face p-stacking interactions.
An interesting complex based on dibenzo-24-crown-10 and diquat was prepared. In its crystal structure the diquat guest lies in the concave cavity provided by two dibenzo-24-crown-8 hosts.
Monopyridinium-based [2]- and [3]-pseudorotaxanes were prepared based on the newly discovered bis(m-phenylene)-32-crown-10/monopyridinium salt and cryptand/monopyridinium salt recognition motifs.
Inspired by the formation of solid-state taco complexes between bis(m-phenylene)-32-crown-10 and paraquat derivatives, we designed and synthesized the first cylindrical bis(crown ether) host for paraquat derivatives and studied its complexation with paraquat.
We prepared three slow-exchange C3-symmetric inclusion complexes based on a newly discovered cryptand/trispyridinium recognition motif, in which 1,3,5-trispyridiniumbenzene salts act as guests.
Finally the application of several new and known recognition motifs in the preparation of a supramolecular poly[3]pseudrotaxane, and the first pseudorotaxane-type supramolecular star-shaped polymer, and the first supramolecular hyperbranched polymer was discussed. / Ph. D.
|
3 |
Design, Preparation and Characterization of Novel Pseudorotaxanes, Semirotaxanes, Rotaxanes, Non-Covalent Supramolecular Polymers and PolycatenanesNiu, Zhenbin 17 October 2011 (has links)
Design and preparation of novel host/guest systems, such as pseudorotaxanes, semirotaxanes, rotaxanes and catenanes, with high association constants, enhanced yields and the abilities to respond to external stimuli are of great importance and significance due to their topological novelty and potential application. The convergence of supramolecular chemistry with polymer science provides an important way to extend the scope of polymer and material sciences by incorporating designed host/guest systems into polymers, and the resulting non-covalently linked supramolecular polymers are expected to have unusual properties due to their unique architectures compared with traditional polymers.
After discovery of bis(meta-phenylene)-32-crown-10 (BMP32C10) derivative/paraquat complexes, for about a quarter century only “taco”-shaped complexes were observed by X-ray crystallography. Here, by the self-assembly of a BMP32C10 bearing two electron-donating groups (carbazoles) with electron-accepting paraquat derivatives, the first [2]pseudorotaxane and the first pseudocryptand-type poly[2]pseudorotaxane based on BMP32C10 were isolated as crystalline solids as shown by X-ray analyses.
The first dual component pseudocryptand-type [2]pseudorotaxanes were designed and prepared via the self-assembly of synthetically easily accessible BMP32C10 pyridyl, quinolyl and naphthyridyl derivatives with paraquat. The formation of the pseudocryptand structures in the complexes remarkably improved the association constants by forming the third pseudo-bridge via H-bonding with the guest and π-stacking of the heterocyclic units.
A pseudocryptand-type [2]pseudorotaxane was formed via the self-assembly of a dipyridyl BMP32C10 derivative and a paraquat derivative. Due to the basicity of the pyridyl group, which forms the third pseudo-bridge of the pseudocryptand, this pseudorotaxane represents the first system with acid-base adjustable association constants, i. e., finite both under acidic and neutral conditions.
The first pseudocryptand-type supramolecular [3]pseudorotaxane was designed and prepared via the self-assembly of a bispicolinate BMP32C10 derivative and a bisparaquat. The complexation behavior was cooperative. In addition, the complex comprised of the BMP32C10 derivative and a cyclic bisparaquat demonstrated strong binding; interestingly, a poly[2]pseudocatenane structure was formed in the solid state for the first time.
Two novel BMP32C10 cryptands, bearing covalent and metal complex linkages, were designed and prepared. By employing the self-assembly of these biscryptands, which can be viewed as AA monomers, and a bisparaquat, which can be viewed as a BB monomer, the first AA/BB-type linear supramolecular polymers with relatively high molecular weights were successfully prepared.
Via the self-assembly of two BMP32C10-based cryptands, bearing covalent and metal complex (ferrocene) linkages, with dimethyl paraquat, novel [3]pseudorotaxanes were formed statistically and anticooperatively, respectively.
From a hydroxyl-functionalized secondary ammonium salt a [2]semirotaxane and a [2]rotaxane were prepared successfully with dibenzo-24-crown-8 (DB24C8). X-ray analysis of a single crystal of the [2]semirotaxane confirmed its semirotaxane nature. In addition, the formation of the [2]semirotaxane can be reversibly controlled by adding KPF6 and 18C6 sequentially. This system affords a way to prepare novel supramolecular polymers.
Dibenzo-30-crown-10 (DB30C10) derivatives and pyridine-based DB30C10 cryptands were prepared by employing the templating method established by our group. A [2]pseudorotaxane was prepared based on DB30C10 diol and paraquat diol. The [3]pseudorotaxane formed via the self-assembly between DB30C10 cryptand and bisparaquat diol occurred in a cooperative manner. In addition, a bromo-functionalized DB30C10 cryptand was successfully designed and prepared. An alkyne-functionalized DB30C10 cryptand was designed and is under preparation; its precursors have been prepared successfully. In the future, based on these functionalized cryptands and paraquat salts, AA and AB type monomers will be prepared. Via the self-assembly between these monomers, non-covalent supramolecular polymers with high molecular weight will be afforded.
A novel DB30C10 cryptand bearing an organometallic bridge, ferrocene, was prepared via 1-(3'-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) coupling of the crown ether diol with ferrocene dicarboxylic acid. The cryptand is dimerized in the solid state via π, π-stacking and hydrogen bonds. The ferrocene-based cryptand formed novel [2]pseudorotaxanes with paraquat and diquat PF₆ salts with association constants (Kₐ) of 1.7 ± 0.1 x 10³ and 4.2 ± 0.3 x 10⁴ M⁻¹ in acetone-d₆, respectively.
In order to prepare linear polycatenanes, the preparation of which represent a real synthetic challenge, a series phenanthroline derivatives were designed and prepared. A “U” shaped monomer was successfully prepared in relative high yield with good solubility. In the future, real linear polycatenanes will be prepared. In addition, a novel diphenanthroline-based BMP32C10 derivative was prepared in high yield and the complexation behavior between it and dimethyl paraquat was studied. / Ph. D.
|
Page generated in 0.0468 seconds