Author : Richard Hooper
Publisher :
ISBN 13 :
Total Pages : pages
Book Rating : 4.:/5 (993 download)
Book Synopsis Synthesis, Characterization and Group Modification of Carbosilane Based Dendrimers by : Richard Hooper
Download or read book Synthesis, Characterization and Group Modification of Carbosilane Based Dendrimers written by Richard Hooper and published by . This book was released on 1997 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Carbosilane dendrimers have been prepared via iterative hydrosilylation/alkenylation reactions using a variety of chlorosilanes (HSiMe3−nC1n)and alkenyl nucleophiles (CH2=CHCH2MgBr and CH2=CHMgBr). Characterization by multinuclear NMR spectroscopy of the stepwise trifurctate dendrimers RED3 (E=Si; R=Ph; D=Dendritic carbosilane fragment) assists end-group counting (NMR, R vs D) and can be related to analogous spheroidal ED4 and hexafunctional E2D6 systems (E=Si or Ge). Typical D units contain (prnSiMe3−n)N Nb linkers; where pr=(CH2)3, N=generation number, Nb=branch multiplicity at silicon. For higher symmetry ED4 and E2D6 systems (and also trifurcate) the Nb=1 (1B series) or Nb=2 (2B series) also allows for end-group counting by proton NMR spectroscopy (Ph:D:Me). 29Si NMR chemical shifts have been developed for topographical mapping of dendritic structure. Peripheral and core substitution reactions have been examined for a series of trifurcate and related Ge2D6 'masked trifurcate' dendrimers. Replacement of end groups with a range of substrates is facilitated by the reactivity of the intermediate silicon chlorine bonds formed by hydrosilylation reactions. Selective removal of the core phenyl group (via triflic acid), or alternatively oxidative Ge-Ge cleavage, allows for unprecedented 'bifunctionalization'; offering routes into dendrimer periphery:core electron transfer ('photon-harvesting') processes. Methodology for a 'rapid-synthesis' of hyperbranched structures has been developed and examined on a range of initial core molecules. Use of multinuclear NMR spectroscopy via comparison with step-wise products, as well as GPC chromatography, gives some insight into the overall architectures produced. Alteration of Si branch point from Nb=2 to Nb=3, using presynthesised 'hypercores' facilitates an alternate method of end group counting for higher symmetry cores. This methodology allows for population counting at large N in dendrimer generation G(N) (D interior vs D periphery).