Metallodendrimers: Structural Diversity and Functional Behavior

Gorman, Christopher B.

doi:10.1002/(sici)1521-4095(199803)10:4<295::aid-adma295>3.0.co;2-n

Cited by 221 publications

(36 citation statements)

References 52 publications

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“…[36] The preparation of these species, starting from MeSiCl 3 (1) as the initial core, includes the following repetitive steps: i) nucleophilic substitution of the silicon-bound chlorides with Me(OEt) 2 SiONa (Scheme 1; molecule 1 as well as dendrimers 3, 5, and 7), and ii) conversion of the silicon-bound ethoxy groups (dendrimers 2, 4,6,8) to chlorides with SOCl 2 , which allows the first step to be repeated (Scheme 1). This approach allows the synthesis of a siloxane dendrimer up to the 4th generation (8,9), possessing a total of 48 EtO± (8) or 48 Cl± (9) end groups. [36] In addition, Muzafarov and co-workers could demonstrate that on subsequent reaction of Si 12 10 (Cl) (5) and Si 48 46 (Cl) (9) with RNa [R = Me 3 CO, (CF 3 (CH 2 ) 2 ) 3 SiO], C 10 H 11 MgBr, or Me 3 SiOSiOMe 2 OH the corresponding surface-functionalized dendrimers Si 12 10 (R) or Si 48 46 (R) [R = Me 3 CO, (CF 3 (CH 2 ) 2 ) 3 SiO, C 10 H 11 , Me 3 SiOSiOMe 2 O] could be synthesized.…”

Section: General Synthetic Methods For the Preparation Of Dendrimersmentioning

confidence: 99%

“…[95] Moreover, peripherally located metal carbonyl building blocks can be introduced via Me 2 SiOCH 2 PPh 2 end-grafted structures, which themselves are formed by alcoholysis of Si± Cl units with HOCH 2 PPh 2 . [78,81] Subsequent reaction of the dendritic molecules Si(O(CH 2 ) 3 SiMe 2 (OCH 2 PPh 2 )) 4 (156) or Si(O(CH 2 ) 3 SiOMe(OCH 2 PPh 2 ) 2 ) 4 (157) with Ni(CO) 4 , Fe 2 (CO) 9 , or M(CO) 5 [78,81] In this respect 1 ® 1-and 1 ® 2-branched carbosiloxane dendrimers can be synthesized (Fig. 9).…”

Section: Reaction Behavior Of Alkoxysilane Dendrimersmentioning

confidence: 99%

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Siloxane and Carbosiloxane Based Dendrimers: Synthesis, Reaction Chemistry, and Potential Applications

Lang

Lühmann

2001

Adv. Mater.

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This article focuses on recent developments made in the field of siloxane and carbosiloxane dendrimers with the silicon atoms as the branching (1 → 2, 1 → 3, or 1 → 4) points. It attempts to treat in a comprehensive way the divergent growth method for the synthesis of Si–O‐ and Si–O–C‐based dendrimers, including their reaction chemistry, their theoretical and physical descriptions, as well as their potential applications in the area of materials science.

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Section: General Synthetic Methods For the Preparation Of Dendrimersmentioning

confidence: 99%

Section: Reaction Behavior Of Alkoxysilane Dendrimersmentioning

confidence: 99%

Siloxane and Carbosiloxane Based Dendrimers: Synthesis, Reaction Chemistry, and Potential Applications

Lang

Lühmann

2001

Adv. Mater.

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“…Incorporation of metal ions into dendritic structures per se has been investigated previously in a variety of cases. [45][46][47][48] Dendrimers containing metal complexes in the core, in the branches, and at the periphery, as well as dendritic systems using metals as branching centers, have been synthesized. [48] However, there have only been a few reports on metal-complexation-induced conformational changes in dendritic ligands.…”

Section: Introductionmentioning

confidence: 99%

Metal‐Induced Chiral Folding of Depsipeptide Dendrimers

Buschhaus¹,

Hampel²,

Hirsch³

2005

Chemistry A European J

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The synthesis and metal complexation of chiral depsipeptide dendrimers 3 and 7 containing an ethylenediaminetetraacetic acid (EDTA) ester‐derived core is reported. The EDTA ester cavity of these dendrimers selectively complexes Zn2+ and Cu2+ ions leading to diastereoselective folding. To elucidate the coordination motif in the resulting “foldamers” of 3‐ZnCl2, 7‐ZnCl2, 3‐CuCl2, and 7‐CuCl2, the coordination behavior of the tetramethyl ester of EDTA (8) has been investigated as a model case. The corresponding complexes 8‐ZnCl2 and 8‐CuCl2 have been structurally characterized by 1H NMR spectroscopy and X‐ray analysis. The complexes involve the inherently chiral octahedral cis‐α coordination motif, in which 8 serves as a tetradentate ligand. In the case of the ZnII complex 8‐ZnCl2, both Δcis‐α(S,S,λ) and Λcis‐α(R,R,λ) stereoisomers were found in the unit cell. For the CuII complex 8‐CuCl2, only one stereoisomer, namely Δcis‐α(S,S,λ) was found in the crystal under investigation. 1H NMR spectroscopy has shown that the same coordination motif is diastereoselectively formed in the chiral Zn2+ dendrimers 3‐ZnCl2 and 7‐ZnCl2. Likewise, the calculated CD spectrum of the Δcis‐α(S,S,λ) stereoisomer of the model complex 8‐CuCl2 shows good agreement with the experimental spectrum of the CuII dendrimers 3‐CuCl2 and 7‐CuCl2, allowing assignment of the absolute configurations of the preferred foldamers as Λcis‐α(R,R,λ) for 3‐CuCl2 and Δcis‐α(S,S,λ) for 7‐CuCl2. This work represents the first example of metal‐complexation‐mediated diastereoselective folding of chiral dendrimers with known absolute configuration.

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“…P{ 1 H} NMR (CD 2 Cl 2 ): δ ϭ Ϫ9.6 (dd, 2 J PP ϭ 26 Hz, 2 J PP ϭ 58 4. Hz, P 0 ), 18.4 (d, 2 J PP ϭ 26 Hz, P 00 ), 47.5 (d, J PP ϭ 58 4.…”

mentioning

confidence: 99%

Varying Topology of Dendrimers − A New Approach toward the Synthesis of Di-Block Dendrimers

Maraval

Sebastián

Ben

et al. 2001

Eur. J. Inorg. Chem.

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Metallodendrimers: Structural Diversity and Functional Behavior

Cited by 221 publications

References 52 publications

Siloxane and Carbosiloxane Based Dendrimers: Synthesis, Reaction Chemistry, and Potential Applications

Siloxane and Carbosiloxane Based Dendrimers: Synthesis, Reaction Chemistry, and Potential Applications

Metal‐Induced Chiral Folding of Depsipeptide Dendrimers

Varying Topology of Dendrimers − A New Approach toward the Synthesis of Di-Block Dendrimers

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