New polyalkynyl dendrons and dendrimers: "click" chemistry with azidomethylferrocene and specific anion and cation electrochemical sensing properties of the 1,2,3-triazole-containing dendrimers.

The synthesis and use of the new tris-alkynyl dendrons 2 to 5 are reported, including the Williamson reaction of 5 with 9-iodo (9), 27-iodo (11), and 81-iodo (12) dendritic cores to yield 27-alkynyl (13), 81-alkynyl (14), and 243-alkynyl (15) dendrimers. So-called "click" reactions of these three dendrimers with azidomethylferrocene (20) give 27-ferrocenyl (16), 81-ferrocenyl (17), and 243-ferrocenyl (18) dendrimers. Electrochemical recognition of oxo-anions (H(2)PO(4)(-) and ATP(2-)) and Pd(2+) cation has been compared using the three polyferrocenyl dendrimers. Derivatization of Pt electrodes with the dendrimers for recognition becomes more facile with increasing size of the dendrimer. This first "click" dendrimer bearing 243-ferrocenyl groups is the best one in the series to obtain robust, recyclable modified Pt electrodes, whereas previous "click" ferrocenyl dendrimers have not been suitable for this purpose.

[1]  D. Astruc,et al.  Metallocenyl dendrimers and their applications in molecular electronics, sensing, and catalysis. , 2008, Accounts of chemical research.

[2]  R. Roy,et al.  Expeditive synthesis of glycodendrimer scaffolds based on versatile TRIS and mannoside derivatives. , 2008, The Journal of organic chemistry.

[3]  G. Newkome,et al.  Recent progress and applications for metallodendrimers , 2007 .

[4]  Anders Hult,et al.  A chemoselective approach for the accelerated synthesis of well-defined dendritic architectures. , 2007, Chemical communications.

[5]  É. Cloutet,et al.  Click assembly of 1,2,3-triazole-linked dendrimers, including ferrocenyl dendrimers, which sense both oxo anions and metal cations. , 2007, Angewandte Chemie.

[6]  D. Astruc,et al.  Metallocenes as references for the determination of redox potentials by cyclic voltammetry Permethylated iron and cobalt sandwich complexes, inhibition by polyamine dendrimers, and the role of hydroxy-containing ferrocenes , 2006 .

[7]  Rachel K. O'Reilly,et al.  Dendrimers Clicked Together Divergently , 2005 .

[8]  C. Hawker,et al.  Structurally diverse dendritic libraries : A highly efficient functionalization approach using Click chemistry , 2005 .

[9]  K. Heuzé,et al.  Metallodendritic catalysis for redox and carbon-carbon bond formation reactions : A step towards green chemistry , 2005 .

[10]  Craig J Hawker,et al.  Efficiency and fidelity in a click-chemistry route to triazole dendrimers by the copper(i)-catalyzed ligation of azides and alkynes. , 2004, Angewandte Chemie.

[11]  M. Glodde,et al.  Designing libraries of first generation AB3 and AB2 self-assembling dendrons via the primary structure generated from combinations of (AB)(y)-AB3 and (AB)(y)-AB2 building blocks. , 2004, Journal of the American Chemical Society.

[12]  Steven P. Brown,et al.  Supramolecular assembly of dendritic polymers elucidated by 1H and 13C solid-state MAS NMR spectroscopy. , 2003, Journal of the American Chemical Society.

[13]  D. Astruc,et al.  Synthesis of five generations of redox-stable pentamethylamidoferrocenyl dendrimers and comparison of amidoferrocenyl- and pentamethylamidoferrocenyl dendrimers as electrochemical exoreceptors for the selective recognition of H2PO4-, HSO4-, and adenosine 5'-triphosphate (ATP) anions: stereoelectroni , 2003, Chemistry.

[14]  S. Lazare,et al.  Construction of giant dendrimers using a tripodal building block. , 2003, Journal of the American Chemical Society.

[15]  D. Astruc,et al.  Supramolecular H-bonded assemblies of redox-active metallodendrimers and positive and unusual dendritic effects on the recognition of H2PO4-. , 2003, Journal of the American Chemical Society.

[16]  D. Astruc.  Organometallic chemistry at the nanoscale. Dendrimers for redox processes and catalysis , 2003 .

[17]  Jason J. Davis,et al.  Anion recognition and redox sensing amplification by self-assembled monolayers of 1,1'bis(alkyl-N-amido)ferrocene. , 2002, Chemical communications.

[18]  Luke G Green,et al.  A stepwise huisgen cycloaddition process: copper(I)-catalyzed regioselective "ligation" of azides and terminal alkynes. , 2002, Angewandte Chemie.

[19]  Morten Meldal,et al.  Peptidotriazoles on solid phase: [1,2,3]-triazoles by regiospecific copper(i)-catalyzed 1,3-dipolar cycloadditions of terminal alkynes to azides. , 2002, The Journal of organic chemistry.

[20]  D. Astruc,et al.  Supramolecular gold nanoparticles for the redox recognition of oxoanions: syntheses, titrations, stereoelectronic effects, and selectivity. , 2002, Journal of the American Chemical Society.

[21]  D. Astruc,et al.  Dendritic catalysts and dendrimers in catalysis. , 2001, Chemical reviews.

[22]  M. G. Finn,et al.  Click Chemistry: Diverse Chemical Function from a Few Good Reactions. , 2001, Angewandte Chemie.

[23]  K. Sharpless,et al.  Click-Chemie: diverse chemische Funktionalität mit einer Handvoll guter Reaktionen , 2001 .

[24]  Joost N. H. Reek,et al.  Übergangsmetallkatalyse mit funktionalisierten Dendrimeren , 2001 .

[25]  J. Reek,et al.  Transition Metal Catalysis Using Functionalized Dendrimers. , 2001, Angewandte Chemie.

[26]  Philip A. Gale,et al.  Erkennung und Nachweis von Anionen: gegenwärtiger Stand und Perspektiven , 2001 .

[27]  Philip A. Gale,et al.  Anion Recognition and Sensing: The State of the Art and Future Perspectives. , 2001, Angewandte Chemie.

[28]  L. Djakovitch,et al.  The First Organometallic Dendrimers: Design and Redox Functions , 2000 .

[29]  G. Newkome,et al.  Suprasupermolecules with Novel Properties: Metallodendrimers. , 1999, Chemical reviews.

[30]  L. Djakovitch,et al.  Organoiron Route to a New Dendron for Fast Dendritic Syntheses Using Divergent and Convergent Methods , 1999 .

[31]  Chungkyun Kim,et al.  Synthesis of carbosilane dendrimers based on tetrakis(phenylethynyl)silane , 1998 .

[32]  P. Beer.  Transition-Metal Receptor Systems for the Selective Recognition and Sensing of Anionic Guest Species , 1998 .

[33]  D. Astruc,et al.  The Dendritic Effect in Molecular Recognition: Ferrocene Dendrimers and Their Use as Supramolecular Redox Sensors for the Recognition of Small Inorganic Anions , 1997 .

[34]  T. Wagner,et al.  Hexakis(but‐3‐inyl)benzol , 1996 .

[35]  T. Wagner,et al.  Hexakis(but-3-ynyl)benzene† , 1996 .

[36]  Nathalie Launay,et al.  Phosphorus-Containing Dendrimers. Easy Access to New Multi-Difunctionalized Macromolecules. , 1996, The Journal of organic chemistry.

[37]  D. Astruc,et al.  Single‐Step Six‐Electron Transfer in a Heptanuclear Complex: Isolation of Both Redox Forms , 1995 .

[38]  D. Astruc,et al.  Einstufiger Sechs-Elektronen-Transfer in einem siebenkernigen Eisenkomplex: Isolierung beider Redoxformen†‡ , 1994 .

[39]  E. Meijer,et al.  Encapsulation of Guest Molecules into a Dendritic Box , 1994, Science.

[40]  Jeffrey S. Moore,et al.  A convenient masking group for aryl iodides , 1991 .

[41]  Jeffrey S. Moore,et al.  Synthesis of rigid dendritic macromolecules: enlarging the repeat unit size as a function of generation, permitting growth to continue , 1991 .

[42]  Gregory R. Baker,et al.  Alkan‐Kaskadenpolymere mit einer Micellen‐Topologie: Micellansäure‐Derivate , 1991 .

[43]  Andrew L. Johnson,et al.  Alkane Cascade Polymers Possessing Micellar Topology: Micellanoic Acid Derivatives , 1991 .

[44]  D. A. Gustowski,et al.  Rationalization of the unusual electrochemical behavior observed in lariat ethers and other reducible macrocyclic systems , 1988 .

[45]  A. Bard,et al.  Electron transfer to and from molecules containing multiple, noninteracting redox centers. Electrochemical oxidation of poly(vinylferrocene) , 1978 .

[46]  R. Huisgen.  Cycloadditionen — Begriff, Einteilung und Kennzeichnung , 1968 .

[47]  R. Huisgen.  Cycloadditions — Definition, Classification, and Characterization , 1968 .

[48]  H. Hiemstra,et al.  CuI‐Catalyzed Alkyne–Azide “Click” Cycloadditions from a Mechanistic and Synthetic Perspective , 2005 .

[49]  Jae Wook Lee,et al.  A facile route to triazole dendrimers via click chemistry linking tripodal acetylene and dendrons , 2005 .

[50]  H. Nishihara,et al.  Preparation of palladium nanoparticles functionalized with biferrocene thiol derivatives and their electro-oxidative deposition , 2001 .