Amalia Rapakousiou

Click dendrimers and triazole-related aspects: catalysts, mechanism, synthesis, and functions. A bridge between dendritic architectures and nanomaterials.

One of the primary recent improvements in molecular chemistry is the now decade-old concept of click chemistry. Typically performed as copper-catalyzed azide-alkyne (CuAAC) Huisgen-type 1,3-cycloadditions, this reaction has many applications in biomedicine and materials science. The application of this chemistry in dendrimer synthesis beyond the zeroth generation and in nanoparticle functionalization requires stoichiometric use of the most common click catalyst, CuSO(4)·5H(2)O with sodium ascorbate. Efforts to develop milder reaction conditions for these substrates have led to the design of polydentate nitrogen ligands. Along these lines, we have described a new, efficient, practical, and easy-to-synthesize catalytic complex, [Cu(I)(hexabenzyltren)]Br, 1 [tren = tris(2-aminoethyl)amine], for the synthesis of relatively large dendrimers and functional gold nanoparticles (AuNPs). This efficient catalyst can be used alone in 0.1% mol amounts for nondendritic click reactions or with the sodium-ascorbate additive, which inhibits aerobic catalyst oxidation. Alternatively, catalytic quantities of the air-stable compounds hexabenzyltren and CuBr added to the click reaction medium can provide analogously satisfactory results. Based on this catalyst as a core, we have also designed and synthesized analogous Cu(I)-centered dendritic catalysts that are much less air-sensitive than 1 and are soluble in organic solvents or in water (depending on the nature of the terminal groups). These multivalent catalysts facilitate efficient click chemistry and exert positive dendritic effects that mimic enzyme activity. We propose a monometallic CuAAC click mechanism for this process. Although the primary use of click chemistry with dendrimers has been to decorate dendrimers with a large number of molecules for medicinal or materials purposes, we are specifically interested in the formation of intradendritic [1,2,3]-triazole heterocycles that coordinate to transition-metal ions via their nitrogen atoms. We describe applications including molecular recognition of anions and cations and the stabilization of transition metal nanoparticles according to a principle pioneered by Crooks with poly(amido amine) (PAMAM) dendrimers, and in particular, the control of structural and reactivity parameters in which the intradendritic [1,2,3]-triazoles and peripheral tripodal tri(ethylene glycol) termini play key roles in the click-dendrimer mediated synthesis and stabilization of gold nanoparticles (AuNPs). By varying these parameters, we have stabilized water-soluble, weakly liganded AuNPs between 1.8 and 50 nm in size and have shown large differences in behavior between AuNPs and PdNPs. Overall, the new catalyst design and the possibilities of click dendrimer chemistry introduce a bridge between dendritic architectures and the world of nanomaterials for multiple applications.

'Click' synthesis and redox properties of triazolyl cobalticinium dendrimers.

The derivatization of macromolecules with redox-stable groups is a challenge for molecular electronics applications. The large majority of redox-derivatized macromolecules involve ferrocenes, and there are only a few reports with cobalticinium. We report here the first click derivatization of macromolecules with the cobalticinium redox group using ethynylcobalticinium hexafluorophosphate, 1. Cu(I) catalysis was used for these selective click metallodendrimer syntheses starting from 1 and providing the tripodal dendron 3 that contains three 1,2,3-triazolylcobalticinium termini and a phenol focal point and the dendrimers of generations 0, 1, and 2 containing 9, 27, and 81 triazolylcobalticinium units for the dendrimers 4, 5, and 6, respectively. Atomic force microscopy (AFM) statistical studies provided the progression of height upon increase of dendrimer generation. Cyclic voltammetry studies in MeCN and dimethylformamide (DMF) show the solvent-dependent reversibility of the Co(III/II) wave (18e/19e) and generation dependent reversibility of the Co(II/I) (19e/20e) wave in DMF. The H2PO4(-) anion is only recognized by the largest metallodendrimer 6 by a significant cathodic shift of the Co(III/II) wave.

Mixed-valent click intertwined polymer units containing biferrocenium chloride side chains form nanosnakes that encapsulate gold nanoparticles.

Polymers containing triazolylbiferrocene are synthesized by ROMP or radical chain reactions and react with HAuCl4 to provide class-2 mixed-valent triazolylbiferrocenium polyelectrolyte networks (observed inter alia by TEM and AFM) that encapsulate gold nanoparticles (AuNPs). With triazolylbiferrocenium in the side polymer chain, the intertwined polymer networks form nanosnakes, unlike with triazolylbiferrocenium in the main polymer chain. By contrast, simple ferrocene-containing polymers do not form such a ferricenium network upon reaction with Au(III), but only small AuNPs, showing that the triazolyl ligand, the cationic charge, and the biferrocenium structure are coresponsible for such network formations.

Synthesis and Redox Activity of “Clicked” Triazolylbiferrocenyl Polymers, Network Encapsulation of Gold and Silver Nanoparticles and Anion Sensing

The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.

Review: Mixed-valent metallodendrimers: design and functions

Various types of mixed-valent metallodendrimers and star-shaped macromolecules containing ferrocenyl, biferrocenyl, or other redox-robust iron groups with rigid or flexible tethers of short and long lengths mostly studied in the authors’ laboratory including the class type in terms of Robin-Day classification and their functions including electrode modification, sensing, and nanoparticle templates are discussed in this mini review. Graphical Abstract

Dendritic Molecular Nanobatteries and the Contribution of Click Chemistry

This article is a mini-review mostly based on the work of the authors’ laboratory on the redox chemistry of metallodendrimers and gold nanoparticles, with emphasis on “click” chemistry. Late transition-metal sandwich complexes possess a rather unique ability to withstand two or three oxidation states without breakdown, especially with permethylated π-cyclopentadienyl or arene ligands. When they are linked to dendritic cores, the assembled nano-systems undergo chemically and electrochemically reversible transfer of a large number of electrons (up to 14,000). These multiple redox processes are useful for nanodevices behaving as nanobatteries for redox sensing, modified electrode surfaces and redox catalysis. Click chemistry was recently disclosed as one of the most powerful means to form such assemblies including both arene-cored and gold nanoparticle-cored dendrimers.

Dentromers, a Family of Super Dendrimers with Specific Properties and Applications

Dentromers (from dentro, δεντρο: tree in Greek), and meros (μεροσ, in greek: part) are introduced as a family of dendrimers constructed according to successive divergent 1 → 3 branching. The smaller dentromers have 27 terminal branches. With alcohol termini they were originally named arborols by Newkome, who pioneered 1 → 3 constructions of dendrimers and dendrons. Giant dentromers have been constructed and decorated in particular with ferrocene and other redox active groups. The synthesis, specific properties, and applications are examined in this mini review article dedicated to Don Tomalia, with an emphasis on dense peripheral packing favoring the functions of encapsulation, redox sensing, and micellar template for catalysis in water and aqueous solvents.