Multiple use of soluble metallodendritic materials as catalysts and dyes

Different sizes of core-functionalized metallodendritic wedges were prepared by anchoring sensor-active arylplatinum(II) sites at the focal point of Fréchet-type polyether dendritic wedges of various generations. The strong color of these metallodendrimers in the presence of SO2 was used to assess the permeability of nanofiltration membranes (molecular weight cut-off of 400 dalton) at ambient pressure. A primary result of these studies is that dendrimers do not have to be exceptionally large for successful retention. Hence, nanofiltration, membrane-capped. immersion vials were developed, which operate as sensor devices when loaded with metallodendrimers with good retention properties. Appropriate substitution of the dye site at the focal point of these metallodendritic wedges by a catalytically active group afforded dendritic catalysts that exhibit essentially the same physical properties (shape, retention) as the corresponding dyefunctionalized dendritic wedges. When this homogeneous catalyst is compartmentalized in membrane-capped vials, a unique and convenient method for its retrieval from product solutions is available. Moreover, such immobilized metallodendritic catalysts can be regenerated and stored for months without losing their activity; this provides access for the development of novel sustainable homogeneous catalysts.     

Design,Synthesis and Self-Assembly of Functional Amphiphilic Metallodendrimers

A new family of alkynylated, amphiphilic dendrimers consisting of amidoamine linkers connected to 5,5′-functionalized 2,2′-bipyridine cores has been developed and evaluated in the formation of metallodendrimers of different generations and in self-assembly protocols. A convergent synthetic strategy was applied to provide dumbbell-shaped amphiphilic dendrimers, where the 2,2′-bipyridine cores could be coordinated to Fe^II centers to afford corresponding metallodendrimers. The ability of the metallic- and non-metallic dendritic structures to self-assemble into functional supramolecular aggregates were furthermore evaluated in aqueous solution. Spherical aggregates with sizes of a few hundred nanometers were generally produced, where controlled disassembly of the metallodendrimers through decomplexation could be achieved.     

Synthesis of triangular metallodendrimers via coordination-driven self-assembly

A new family of 60° dendritic di-Pt(II) acceptor tectons have been successfully designed and synthesized, from which a series of novel "three-component" triangular metallodendrimers were prepared via [3 + 3] coordination-driven self-assembly. The structures of newly designed triangular metallodendrimers are characterized by multinuclear NMR ((1)H and (31)P), (1)H DOSY NMR, mass spectrometry (CSI-TOF-MS), and elemental analysis. The shape and size of all supramolecular dendritic triangles were investigated with PM6 semiempirical molecular orbital methods.     

Synthesis,photophysical, and electrochemical properties of triazolyl dendrimers with thiazolylchalcone surface unit

Synthesis of novel triazolyl dendrimers with thiazolylchalcone surface group and triazole as bridging unit has been achieved in good yields by click chemistry through convergent approach. All the triazolyl dendrimers showed an absorption band between 293 and 336?nm and an emission band between 430 and 435?nm. The intensity of absorption and emission bands increases on increasing the number of dendritic wedges and triazole units. Triazolyl dendrimers exhibited quasi-reversible behavior in cyclic voltammetry. A shift in the reversible potential was observed in cyclic voltammetry on increasing the dendritic wedges in the triazolyl dendrimers.     

Self-assembly of molecular dumbbells into organized bundles with tunable size

Dumbbell-shaped molecules consisting of three biphenyls connected through vinyl linkages as a conjugated rod segment and aliphatic polyether dendritic wedges with different cross-sections (i.e., dibranch (1), tetrabranch (2) and hexabranch (3)) were synthesized and characterized. The molecular dumbbells self-assemble into discrete bundles that organize into three-dimensional superlattices. Molecule 1, based on a dibranched dendritic wedge, organizes into primitive monoclinic-crystalline and body-centered, tetragonal liquid crystalline structures, while molecules 2 and 3, based on tetra- and hexabranched dendritic wedges, respectively, form only body-centered, tetragonal liquid crystalline structures. X-ray diffraction experiments and density measurements showed that the rod-bundle cross-sectional area decreases with increasing cross-section of the dendritic wedges. The influences of supramolecular structure on the bulk-state optical properties were investigated by measuring the UV/Vis absorption and steady state fluorescence spectroscopies. As the cross-section of the dendritic wedge of the molecule increases, the absorption and emission maxima shift to higher energy. This can be attributed to a quantum size effect of the three-dimensionally confined nanostructure.     

Microenvironment-switchable singlet oxygen generation by axially-coordinated hydrophilic ruthenium phthalocyanine dendrimers

A series of new metallodendrimers built around a ruthenium phthalocyanine core has been prepared. Employing a convergent synthetic strategy, pyridine-containing ligands were prepared and then assembled onto the ruthenium phthalocyanine through axial ligand coordination. The growing shell of oligoethylene glycol chains surrounding the lipophilic core allows solubilisation in water. Photophysical studies show that all the metallodendrimers are strongly phosphorescent and the deactivation pathway of their triplet state depends on the medium in which the compounds are dissolved. On one hand, quenching of the triplet state by the dendritic shell is observed and found to be substantially enhanced in aqueous media. On the other, the dendrimer shields the phthalocyanine from oxygen. This notwithstanding, the phthalocyanines are able to generate singlet oxygen in less polar environments such as in CHCl(3) or THF solution, while in water the generation of singlet oxygen is almost completely switched off.     

Coordination‐Driven Self‐Assembly of Carbazole‐Based Metallodendrimers with Generation‐Dependent Aggregation‐Induced Emission Behavior

A new family of 120° carbazole‐based dendritic donors D1 – D3 have been successfully designed and synthesized, from which a series of novel supramolecular carbazole‐based metallodendrimers with well‐defined shapes and sizes were successfully prepared by [2+2] and [3+3] coordination‐driven self‐assembly. The structures of newly designed rhomboidal and hexagonal metallodendrimers were characterized by multinuclear NMR (¹H and ³¹P) spectroscopy, ESI‐TOF mass spectrometry, FTIR spectroscopy, and the PM6 semiempirical molecular orbital method. The fluorescence emission behavior of ligands D1 – D3 , rhomboidal metallodendrimers R1 – R3 , and hexagonal metallodendrimers H1 – H3 in mixtures of dichloromethane and n‐hexane with different n‐hexane fractions were investigated. The results indicated that D1 – D3 featured typical aggregation‐induced emission (AIE) properties. However, different from ligands D1 – D3 , metallodendrimers R1 – R3 and H1 – H3 presented interesting generation‐dependent AIE properties. Furthermore, evidence for the aggregation of these metallodendrimers was confirmed by a detailed investigation of dynamic light‐scattering, Tyndall effect, and SEM. This research not only provides a highly efficient strategy for constructing carbazole‐based dendrimers with well‐defined shapes and sizes, but also presents a new family of carbazole‐based dendritic ligands and rhomboidal and hexagonal metallodendrimers with interesting AIE properties.     

FeCp]+-induced hexafunctionalization of hexamethylbenzene with dendrons for the direct synthesis of redox-active iron-centered metallodendrimers

Phenol tri- and nonaallyl dendrons (3 and 7, respectively) were functionalized at the focal position to give the new triallyl dendrons 4 and 6 and the nonaallyl dendrons 11 and 13 that contain a iodoalkyl or a bromobenzyl termini. All these dendrons were used for the [FeCp]+-induced hexafunctionalization of hexamethylbenzene in [FeCp(eta6-C6Me6)][PF6] (1) under mild conditions in the presence of KOH. These reactions directly yielded the 18-allyl and 54-allyl dendrimers 9, 10, and 14 with a [FeCp(eta6-arene)]+ unit located at the dendrimer core. Cyclic voltammetry studies were recorded in THF and DMF with these metallodendrimers and compared with those of analogous dendrimers or complexes of smaller size that contain a [FeCp(eta6-arene)]+ unit at the core. The decreased rate of heterogeneous electron transfer when the dendritic size increases first disclosed by Diederich and Gross is confirmed. The variation of the redox potential of the Fe(II/I) redox system with increasing dendritic size is negligible even in a solvent of high dielectric constant such as DMF. This trend is attributed to fact that the involved "redox" orbital is buried on the metal center, well protected by the shell of alkyl chains (electron-reservoir nature), unlike in ferrocene. The chemical irreversibility increases in THF as the dendrimer size increases, due to more facile ligand substitution with THF at the 19-electron level when the chain bulk increases.     

The Convergent Route to Globular Dendritic Macromolecules: A Versatile Approach to Precisely Functionauzed Three-Dimensional Polymers and Novel Block Copolymers

The convergent growth approach to dendritic macromolecules is a versatile method for the preparation of globular molecules with highly controlled three-dimensional architectures. The method, inspired from a classical organic disconnection approach, starts growth of the globular dendrimer at what will become its chain-ends and proceeds toward what will become its center. The convergent growth has been applied to the preparation of a number of unconventional dendritic block copolymers as well as hybrid globular-linear copolymers that are not readily accessed by other routes. Control of the chemistry and the precise location of the chain-ends in convergent dendrimers is essential for the preparation of micellar, amphiphilic, dipolar, or other structures that may be useful in applications as varied as drug delivery and molecular devices.     

An efficient route for the synthesis of hyperbranched polymers and dendritic building blocks based on urea linkages

A highly efficient synthetic route, based on the quantitative reaction between amine and isocyanate functionalities, was used successfully for the synthesis of hyperbranched polymers and dendritic building blocks based on urea linkages. The thermal decomposition of 3,5‐diamino benzoyl azide or 5‐amino isophthaloyl azide generated in situ the corresponding phenyl isocyanates, which were then polymerized to give wholly aromatic hyperbranched polyureas. Hyperbranched polyurea with amine chain ends was soluble in common organic solvents. The degree of branching, as calculated with ¹H NMR, was 0.55. Diethyl 5‐amino isophthalate and Boc‐protected 5‐amino isophthaloyl azide were used for the successful stepwise synthesis of dendritic wedges based on urea linkages. The thermal generation of the isocyanate functionality with gaseous nitrogen as the side product and its quantitative reaction with amine groups were the salient features of this convergent synthesis. This eliminated the use of chromatographic purification, an inherent part of other convergent growth approaches, and made it a very efficient synthetic route for the synthesis of dendritic wedges. The products were characterized by ¹H NMR, ¹³C NMR, and electron spray mass spectroscopy (ESMS) techniques. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1295–1304, 2001     

Synthesis and photophysical,antibacterial studies of some novel molecular tweezers

Zeroth and first generation dendritic wedges with thiophene amide as surface group and 1, 2, 3-triazole as bridging unit which can function as molecular tweezers are synthesised by both convergent and divergent approaches. All the synthesised dendritic wedges displayed the absorbance band between 256 and 294 nm and fluorescence maximum between 357 and 528 nm supporting their self complementary property. Dendritic wedge 5 showed better antibacterial activity than other dendritic wedges in the assay against the human pathogens viz Staphylococcus aureus, Escherichia coli, Bacillus cereus and Klebsiella pneumonia and the dentritic wedge 5 was also effective in the computational molecular docking studies.     

Coordination-driven self-assembly of metallodendrimers possessing well-defined and controllable cavities as cores

The design and self-assembly of novel cavity-cored metallodendrimers via noncovalent interactions are described. By employing [G0]-[G3] 120 degrees ditopic donor linkers substituted with Fréchet-type dendrons and appropriate rigid di-Pt(II) acceptor subunits, [G0]-[G3]-rhomboidal metallodendrimers and [G0]-[G3]-hexagonal, "snowflake-shaped" metallodendrimers with well-defined shape and size were prepared under mild conditions in high yields. The assemblies were characterized with multinuclear NMR ((1)H and (31)P), mass spectrometry (ESI-MS and ESI-FT-ICR-MS), and elemental analysis. Isotopically resolved mass spectrometry data support the existence of the metallodendrimers with rhomboidal and hexagonal cavities, and NMR data are consistent with the formation of all ensembles. The structures of [G0]- and [G1]-rhomboidal metallodendrimers were unambiguously confirmed via single-crystal X-ray crystallography. The shape and size of two [G3]-hexagonal metallodendrimers were investigated with MM2 force-field modeling.     

Star-shaped electrochemiluminescent metallodendrimers with central polypyridyl Ru(II) complexes: Synthesis and their photophysical and electrochemical properties

Several dendritic bridging ligands were designed and synthesized to develop more sensitive and efficient electrochemiluminescent (ECL) polynuclear Ru(II) complexes. Various types of novel two-armed, four-armed and six-armed tris(bipyridyl)ruthenium core dendrimers were synthesized by coordinating dendritic polybipyridyl ligands with Ru(II) complexes, and the effect of the ligand and the dendritic network on the ECL characteristics were studied. Their electrochemical redox potentials, UV, photoluminescence (PL), and relative ECL intensities were also investigated in detail. The synthesized metallodendrimers exhibited strong metal-to-ligand charge transfer (MLCT) absorption at 428-451 nm and emission at 591-601 nm. Most of the newly synthesized metallodendrimers showed enhanced ECL intensities compared to the reference complex, [Ru(o-phen)₃](PF₆)₂. In particular, the ECL intensities of the six-armed heptanuclear ruthenium complexes were almost four times greater than that of [Ru(o-phen)₃]²⁺. These metallodendrimers could be utilized as efficient ECL materials and light emitting devices.     

Large oligosaccharide-based glycodendrimers

Carbohydrate-based dendritic structures composed of 21 and 27 monosaccharide residues have been synthesized in a convergent manner from trisaccharide building blocks. The oligosaccharide AB2 monomers are based on a maltosyl beta(1-->6)galactose structure, which has been modified to include two methylamino groups at the primary positions of the glucosyl residues. Reductive alkylation of the secondary amino groups, with the innate formyl function of a second oligosaccharide monomer, allows for the chemoselective construction of dendritic wedges, while employing a minimal number of protecting groups. The first-generation dendron can be coupled either to another AB2 monomer, to give a second-generation dendron, or to a tris[2-(methylamino)ethyl]amine-based core moiety, to provide a carbohydrate-based dendrimer. Alternating alpha- and beta-glucosyl residues in the monomers and dendrons, simplifies 1H NMR spectra as a consequence of spreading out the anomeric proton signals. Monomers and dendrons were characterized by extensive one- and two-dimensional NMR spectroscopy in addition to FAB, electrospray, and MALDI-TOF mass spectrometry. Molecular dynamics simulations revealed similar conformations in the dendrons as in the isolated trisaccharide repeating units.     

New iron bis(imino)pyridyl complexes containing dendritic wedges for alkene oligomerisation

The synthesis, characterisation and catalytic behaviour of new iron bis(imino)pyridyl complexes containing dendritic wedges, as well as the synthesis of bis(para-hydroxyphenylimino)pyridines is described. The hydroxyl functionality of the bis(para-hydroxyphenylimino)pyridines was used to attach dendritic wedges of the carbosilane type as well as the benzylphenyl ether type. After attachment of the dendritic wedges, complexation of these ligands to iron(II) chloride was achieved. The resulting dendritically functionalised bis(imino)pyridyl iron complexes were tested in the catalytic oligomerisation of ethene.     

Ordered nanostructures from self-assembly of rod–coil oligomers with n-shaped rod and dendritic poly(ethylene oxide) coil segment

The n-shaped rod–coil molecules consisting of an anthracene unit and two biphenyl groups connected by acetylenyl bonds as a conjugated rod segment and dendritic poly(ethylene oxide)s with different cross-sectional areas were synthesised. These new molecular structures were characterised by using ¹H NMR and MALDI-TOF-MS. The self-assembly of these molecules in the bulk state and in aqueous solution was investigated using differential scanning calorimetry, X-ray diffraction and transmission electron microscopy (TEM). In the bulk state, molecule 1a with a linear coil segment, self-organised into lamellar crystalline structures, whereas molecules 1b and 1c with di- and tetra-branched dendritic wedges did not solidify at room temperature. Dynamic light scattering and TEM experiments reveal that in aqueous solution, the molecules exhibit a strong tendency to organise into the thread-like fibres along the axial direction of cylindrical micelles or into the wide fibroid bundles via the aggregation of cylindrical micelles as the cross-sectional area of the dendritic coil segments increases.     

The Usefulness of Trivalent Phosphorus for the Synthesis of Dendrimers

Dendrimers are hyperbranched macromolecules, which are synthesized step-by-step by the repetition of a series of reactions. While many different types of dendrimers are known, this review focusses on the use of trivalent phosphorus derivatives (essentially phosphines and phosphoramidites) for the synthesis of dendrimers. The first part presents dendrimers constituted of phosphines at each branching point. The other parts display the use of trivalent phosphorus derivatives during the synthesis of dendrimers. Different types of reactions have been applied to phosphines. The very first examples of phosphorus-containing dendrimers were obtained by the alkylation of phosphines. Then, several families of dendrimers were elaborated by reaction of phosphoramidites. Such a type of reaction is the base of the solid phase synthesis of oligonucleotides; it has been applied in particular for the synthesis of dendrimers constituted of oligonucleotides. Finally, the Staudinger reaction between phosphines and azides afforded different families of dendrimers, and was at the origin of accelerated methods of synthesis of dendrimers. Besides, the reactivity of the P=N-P=S linkages created by this reaction led to very original dendritic structures.     

Dendritic multiporphyrin arrays as light-harvesting antennae: effects of generation number and morphology on intramolecular energy transfer

A series of star- and cone-shaped dendritic multiporphyrin arrays, (nPZn)4PFB and (nPZn)1PFB, respectively, that contain energy-donating dendritic zinc porphyrin (PZn) wedges of different numbers (n = 1, 3, and 7) of the PZn units, attached to an energy-accepting free-base porphyrin (PFB) core, were synthesized by a convergent growth approach. For the cone-shaped series ((nPZn)1PFB), the efficiency of energy transfer (phi ENT) from the photoexcited PZn units to the focal PFB core, as evaluated from the fluorescence lifetimes of the PZn units, considerably decreased as the generation number increased: (1PZn)1PFB (86%), (3PZn)1PFB (66%), and (7PZn)1PFB (19%). In sharp contrast, the star-shaped series ((nPZn)4PFB) all showed high phi ENT values: (1PZn)4PFB (87%), (3PZn)4PFB (80%), and (7PZn)4PFB (71%). Energy transfer efficiencies of (3PZn)4-ester-PFB, (1PZn)4-ester-PFB, and (3PZn)1-ester-PFB, whose dendritic PZn wedges are connected by an ester linkage to the PFB core, were almost comparable to those of the corresponding ether-linked versions. Fluorescence depolarization (P) studies showed much lower P values for star-shaped (7PZn)4PFB and (3PZn)4PFB than cone-shaped (7PZn)1PFB and (3PZn)1PFB, respectively, indicating a highly efficient energy migration among the PZn units in the star-shaped series. Such a morphology-assisted photochemical event is probably responsible for the excellent light-harvesting activity of large (7PZn)4PFB molecules.     

Dendritic BINOL ligands for asymmetric catalysis: effect of the linking positions and generations of the dendritic wedges on catalyst properties

Three types of new chiral BINOL ligands (2, 3 and 4) bearing dendritic wedges have been synthesized through coupling reaction between 3-hydroxymethyl-2,2′-bis(methoxymethyl)-1,1′-binaphthol (7), 6,6′-dihydroxymethyl-2,2′-bis(methoxymethyl)-1,1′-binaphthol (12), 6-hydroxymethyl-2,2′-bis(methoxymethyl)-1,1′-binaphthol (15) and Fréchet-type polyether dendritic benzyl bromide, followed by deprotection of methoxymethyl groups by ⁱPrOH/HCl, respectively. These new ligands obtained were assessed in enantioselective Lewis acid-catalyzed addition of diethylzinc to benzaldehyde. Compared to the enantioselectivity observed with dendrimer 1 bearing the dendritic wedges at 3,3′-positions of the binaphthyl backbone, higher enantioselectivity for all these ligands was observed. Difference in the effect of linking positions and generations on enantioselectivity and/or activity for all three kinds of dendritic ligand-derived catalysts was observed. Among these dendritic ligands, (R)-3/Ti(IV) catalyst with the dendritic wedges at 6,6′-positions of BINOL gave the highest enantioselectivity (up to 87% ee).     

以尼罗红为探针对新型两亲性树枝形聚合物微环境的研究

本工作合成了一系列外围以三缩四乙二醇单甲醚修饰的烷基芳醚骨架两亲性树枝形聚合物Gn(n=0—3),化合物通过了¹H-NMR,IR和MALDI-TOF-MS的表征.利用吸收光谱,稳态和时间分辨荧光光谱研究了水溶液中Gn对尼罗红分子的增溶作用以及Gn内部微环境的极性.研究结果表明,高代数树枝形聚合物Gn对尼罗红具有更好的增溶效果.1—3代树枝形聚合物Gn内部疏水孔腔微环境极性随代数增加而逐渐降低,G1和G2树枝形聚合物具有相似的微环境极性,而由于构象的变化使G3具有更加疏水的微环境.