Search results for "Molecular chemistry"
showing 10 items of 1103 documents
Thermo-, piezo-, photo- and chemo-switchable spin crossover iron(II)-metallocyanate based coordination polymers
2011
Abstract The design of coordination polymers (CPs) with switch and memory functions is an important subject of current interest in the search for new advanced materials with potential applications. Implementation of CPs with electronically labile iron(II) building blocks able to undergo cooperative spin crossover (SCO) behavior is a singular approach to this end. This review provides an up to date survey of a new generation of iron(II)-metallocyanate based spin crossover coordination polymers (SCO-CPs) developed during the last decade. These new solids feature structural diversity, supramolecular isomerism, interpenetrating frameworks, structure flexibility, reversible solid-state chemical …
Interaction of aminomethylated resorcinarenes with rhodamine B
2009
The interaction of aminomethylated resorcinarenes with a red xanthene dye, rhodamine B, was investigated in chloroform, methanol and chloroform–methanol solutions using UV-vis, NMR and fluorescence spectroscopy. Aminomethylated resorcinarenes 1 and 2 shift the rhodamine B equilibrium from the zwitterion to the lactone form unlike reference compounds 3 and 4, which do not contain tertiary amino groups at the upper rim, giving an example of how supramolecular hosts can influence the equilibrium of rhodamine B isomers.
Superchiral Pd 3 L 6 Coordination Complex and Its Reversible Structural Conversion into Pd 3 L 3 Cl 6 Metallocycles
2015
Large, non-symmetrical, inherently chiral bispyridyl ligand L derived from natural ursodeoxycholic bile acid was used for square-planar coordination of tetravalent Pd(II) , yielding the cationic single enantiomer of superchiral coordination complex 1 Pd3 L6 containing 60 well-defined chiral centers in its flower-like structure. Complex 1 can readily be transformed by addition of chloride into a smaller enantiomerically pure cyclic trimer 2 Pd3 L3 Cl6 containing 30 chiral centers. This transformation is reversible and can be restored by the addition of silver cations. Furthermore, a mixture of two constitutional isomers of trimer, 2 and 2', and dimer, 3 and 3', can be obtained directly from …
Hierarchical structure formation of cylindrical brush polymer-surfactant complexes.
2009
The complex formation of cylindrical brush polymers with poly(l-lysine) side chains (PLL) and sodium dodecyl sulfate (SDS) can induce a helical conformation of the cylindrical brush polymer in aqueous solution (Gunari, N.; Cong, Y.; Zhang, B.; Fischer, K.; Janshoff, A.; Schmidt, M. Macromol. Rapid Commun. 2008, 29, 821-825). Herein, we have systematically investigated the influence of surfactant, salt, and pH on the supramolecular structure formation. The cylindrical brush polymers and their complexes with surfactants were directly visualized by atomic force microscopy in air and in aqueous solution. The alkyl chain length (measured by the carbon number, n) of the surfactant plays a key rol…
Structure and luminescence properties of supramolecular polymers of amphiphilic aromatic thioether–peptide conjugates in water
2019
We present the preparation of luminophore–peptide conjugates that self-assemble into supramolecular polymers in neutral buffer. To this end, we have prepared a small library of six conjugates with varying substitution patterns of the aromatic thioethers, as well as varying amino acid sequences. The latter have allowed us to tune the thermodynamic driving force for self-assembly and probe their photoluminescent properties either in the monomeric or polymeric state, while fully avoiding selective solvent techniques or organic solvent mixtures. All of the supramolecular structures were characterised with transmission electron microscopy, circular dichroism measurements, as well as steady-state…
Non-Centrosymmetric Homochiral Supramolecular Polymers of Tetrahedral Subphthalocyanine Molecules
2015
This is the peer reviewed version of the following article: Angewandte Chemie - International Edition 54.8 (2015): 2543-2547, which has been published in final form at http://dx.doi.org/10.1002/anie.201411272. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving
Supramolecular chirality in organogels: a detailed spectroscopic, morphological, and rheological investigation of gels (and xerogels) derived from al…
2010
This Article addresses the formation of chiral supramolecular structures in the organogels derived from chiral organogelator 1R (or 2R), and its mixtures with its enantiomer (1S) and achiral analogue 3 by extensive circular dichroism (CD) spectroscopic measurements. Morphological analysis by atomic force microscopy (AFM) and scanning electron microscopy (SEM) were complemented by the measurements of their bulk properties by thermal stability and rheological studies. Specific molecular recognition events (1/3 vs 2/3) and solvent effects (isooctane vs dodecane) were found to be critical in the formation of chiral aggregates. Theoretical studies were also carried out to understand the interact…
Binding properties of heptakis-(2,6-di-O-methyl)-β-cyclodextrin and mono-(3,6-anhydro)-β-cyclodextrin: a polarimetric study
2011
The binding constants for the inclusion complexes formed between heptakis-(2,6-di-O-methyl)-β-cyclodextrin (MβCD) and mono-(3,6-anhydro)-β-cyclodextrin (AβCD) with a set of suitably selected organic guests, were measured by means of polarimetry. Measurements were carried out at various pH values in order to ensure the correct protonation state for ionizable guests. Experimental data suggest that the binding properties of MβCD may be rationalized considering the less polar and more hydrophobic character of the cavity, although similar variations in conformational/dynamic behaviour occur as for native βCD. On the other hand, AβCD shows some similarities with αCD, due to the significant distor…
Direct Visualization of Pyrrole Reactivity upon Confinement within a Cyclodextrin Metal–Organic Framework
2019
Metal–organic frameworks can be used as porous templates to exert control over polymerization reactions. Shown here are the possibilities offered by these crystalline, porous nanoreactors to capture highly-reactive intermediates for a better understanding of the mechanism of polymerization reactions. By using a cyclodextrin framework the polymerization of pyrrole is restricted, capturing the formation of terpyrrole cationic intermediates. Single-crystal X-ray diffraction is used to provide definite information on the supramolecular interactions that induce the formation and stabilization of a conductive array of cationic complexes.
Thermodynamics of cyclodextrin-star copolymer threading-dethreading process
2015
We investigated the interactions of a star-like copolymer with cyclodextrins (CD) with different cavity size. Direct measurements of thermodynamic properties were done, and the application of proper molecular models was useful for the interpretation of the involved phenomena. The CD–copolymer inclusion complexes were characterized by isothermal titration calorimetry. The copolymer aggregation induced by temperature was investigated by differential scanning calorimetry, volume and compressibility measurements. The behavior of the ternary T1107/CD/water mixture was interpreted considering competing equilibria. The investigated systems showed an interesting temperature responsive behavior so t…