Self-assembly of supramolecular architectures and polymers by orthogonal metal complexation and hydrogen-bonding motifs

A modular construction kit with two orthogonal noncovalent binding sites for self-assembly of supramolecular architectures is presented. The heteroditopic building blocks contain a terpyridine (tpy) unit for coordination of metal ions and a Hamilton receptor for multiple H-bonding of cyanuric acid derivatives. The association constants of ligand binding of M(II) complexes (M=Ru, Zn, Fe, and Pt) with a dendritic end cap were determined to be in the range of 10(2) and 10(4) L mol(-1) in chloroform. The capabilities for binding of metal ions were investigated by (1)H NMR and UV/Vis spectroscopy. The Fe complexes are most appropriate for the generation of discrete and high-ordered architectures due to their strong tendency to form FeL(2) complexes. Superstructures are readily formed in a one-pot procedure at room temperature. No mutual interactions between the orthogonal binding motifs were observed, and this demonstrates the highly specific nature of each binding process. Decomplexation experiments were carried out to examine the reversibility of Fe-tpy coordination. Substitution of the terminal end cap with a homoditopic bis-cyanurate linkage leads to formation of an iron-containing supramolecular strand. Formation of coordination polymers was confirmed by viscosity measurements. The supramolecular polymer strands can be reversibly cleaved by addition of a terminating cyanuric acid building block, and this proves the dynamic nature of this noncovalent polymerization process.     

Supramolecular Nanoassemblies of an Amphiphilic Porphyrin–Cyclodextrin Conjugate and Their Morphological Transition from Vesicle to Network

An amphiphilic compound, 5‐(4′‐dodecyloxyphenyl)‐10,15,20‐tri(permethyl‐β‐CD)‐modified Zn^II–porphyrin ( 1 ; β‐CD=β‐cyclodextrin), was synthesized by means of the click reaction of an alkylated Zn–porphyrin derivative with 6‐deoxy‐6‐azidopermethyl‐β‐CD. The complexation between 1 and tetrasodium tetraphenylporphyrintetrasulfonate ( 5 ) with different molar ratios led to the formation of two distinctly different nanoarchitectures, which were proven to be vesicle and network aggregates, respectively, by using dynamic light scattering, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. On the basis of the results of the time‐dependent TEM studies, fluorescence, and NMR spectroscopic measurements, we have determined that the mechanism of the morphology transition from vesicles to networks is controlled by the stepwise complexation of 1 with 5 . Furthermore, these supramolecular nanoarchitectures show the controlled‐ release property of doxorubicin as potential candidates for drug delivery.     

From molecular to macroscopic engineering: shaping hydrogen-bonded organic nanomaterials

The self‐assembly and self‐organization behavior of chromophoric acetylenic scaffolds bearing 2,6‐bis(acetylamino)pyridine ( 1 , 2 ) or uracyl‐type ( 3 – 9 ) terminal groups has been investigated by photophysical and microscopic methods. Systematic absorption and luminescence studies show that 1 and 2 , thanks to a combination of solvophilic/solvophobic forces and π–π stacking interactions, undergo self‐organization in apolar solvents (i.e., cyclohexane) and form spherical nanoparticles, as evidenced by wide‐field optical microscopy, TEM, and AFM analysis. For the longer molecular module, 2 , a more uniform size distribution is found (80–200 nm) compared to 1 (20–1000 nm). Temperature scans in the range 283–353 K show that the self‐organized nanoparticles are reversibly formed and destroyed, being stable at lower temperatures. Molecular modules 1 and 2 were then thoroughly mixed with the complementary triply hydrogen‐bonding units 3 – 9 . Depending on the specific geometrical structure of 3 – 9 , different nanostructures are evidenced by microscopic investigations. Combination of modules 1 or 2 with 3 , which bears only one terminal uracyl unit, leads to the formation of vesicular structures; instead, when 1 is combined with bis‐uracyl derivative 4 or 5 , a structural evolution from nanoparticles to nanowires is observed. The length of the wires obtained by mixing 1 and 4 or 1 and 5 can be controlled by addition of 3 , which prompts transformation of the wires into shorter rods. The replacement of linear system 5 with the related angular modules 6 and 7 enables formation of helical nanostructures, unambiguously evidenced by AFM. Finally, thermally induced self‐assembly was studied in parallel with modules 8 and 9 , in which the uracyl recognition sites are protected with tert‐butyloxycarbonyl (BOC) groups. This strategy allows further control of the self‐assembly/self‐organization process by temperature, since the BOC group is completely removed on heating. Microscopy studies show that the BOC‐protected ditopic modules 8 self‐assemble and self‐organize with 1 into ordered linear nanostructures, whereas BOC‐protected tritopic system 9 gives rise to extended domains of circular nano‐objects in combination with 1 .     

Organogold(III) supramolecular polymers for anticancer treatment

Gold cures: the depicted gold(III) complex self-assembles into supramolecular polymers which form nanofibrillar networks that display sustained cytotoxicity and can also act as carriers for other cytotoxic agents.     

A versatile bis-porphyrin tweezer host for the assembly of noncovalent photoactive architectures: a photophysical characterization of the tweezers and their association with porphyrins and other guests

A bis(Zn(II)-porphyrin) tweezer host with anthracene components as apex and side-arms has been synthesized. Mono- (pyridine) and bidentate (4,4'-bipyridine) guests were used as models for single and double axial coordination inside the cavity, respectively. A series of dipyridylporphyrin guests with different substitution patterns and excited-state energy levels have association constants with the tweezers that are of the order of 10(6) M(-1), which is indicative of complexation with the inside of the cavity. This complexation can only occur upon an important distortion of the cavity that opens the bite by about 30 %. This characteristic, in conjunction with their ability to reduce the bite distance by rotation around single bonds, makes these porphyrin tweezers amongst the most versatile so far reported, with tuning of the bite distance in the range of approximately 5-20 Angstroms. Energy transfer to the free-base guest within the triporphyrin complex is nearly quantitative (95-98 %) and the rates of transfer are consistent with a F?rster mechanism that is characterized by a reduced orientation factor.