Octakis(3‐azidopropyl)octasilsesquioxane: A Versatile Nanobuilding Block for the Efficient Preparation of Highly Functionalized Cube‐Octameric Polyhedral Oligosilsesquioxane Frameworks Through Click Assembly

Trastoy, Beatriz; Pérez‐Ojeda, M. Eugenia; Sastre, R.; Chiara, José Luis

doi:10.1002/chem.200902422

Cited by 70 publications

(57 citation statements)

References 98 publications

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“…[11,14a,c,d] The versatility of this approach have been demonstrated in the preparation of the dye-POSS cluster 4 using the alkyne-substituted BDP fluorescent dye 3 (Scheme 2). [11] We have now studied the monofunctionalization of octa-azide 2 with the alkyne-substituted BDP dye 3 (Scheme 3), which we used previously for the preparation of dye-POSS cluster 4. This reaction would afford a POSS derivative 5 labeled with a single fluorescent probe and containing seven additional reactive azide groups ready for further functionalization with any molecule of interest having a terminal alkynyl group.…”

Section: Resultsmentioning

confidence: 99%

Click Assembly of Dye‐Functionalized Octasilsesquioxanes for Highly Efficient and Photostable Photonic Systems

Pérez‐Ojeda

Trastoy

López‐Arbeloa

et al. 2011

Chemistry A European J

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New hybrid organicinorganic dyes based on an azidefunctionalized octasilsesquioxane (POSS) as inorganic part and a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP) chromophore as the organic component have been synthesized by copper(I)-catalyzed 1,3-dipolar cycloaddition of azides to alkynes. We have studied the effect of the linkage group of BDP to the POSS unit and the degree of functionalization of this inorganic core on the optical properties by comparison with model dyes. The high fluorescence ability of the BDP dye is preserved in spite of the linked chain at its meso position and even after attaching one BDP to the POSS core. The laser action of the new dyes has been analyzed under transversal pumping at 532 nm in both liquid phase and when incorporated into solid polymeric matrices. The new hybrid dye exhibits high lasing efficiency of up to 56% with high photostability, with its laser output remaining at the initial value after 4×10 5 pump pulses in the same position of the sample at 30 Hz repetition rate. Nonetheless, the functionalization of the POSS core with eight fluorophores leads to dye aggregation, as quantum mechanics simulation reveals, worsening the optical properties and extinguishing the laser action. The new hybrid systems based on dye-linked POSS nanoparticles opens up the possibility of using these new photonic materials as alternative sources for optoelectronic devices, competing with dendronized or grafted polymers.

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Section: Resultsmentioning

confidence: 99%

Click Assembly of Dye‐Functionalized Octasilsesquioxanes for Highly Efficient and Photostable Photonic Systems

Pérez‐Ojeda

Trastoy

López‐Arbeloa

et al. 2011

Chemistry A European J

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“…However, at the onset of our work, there was only a single example reported in the literature on the use of NfN 3 for the synthesis of an organic azide from a primary amine. [22] In our previous work, [12] we found that NfN 3 afforded higher and more reproducible yields of 2 (60-73%, which accounts for > 94% yield per amino group) than TfN 3 , under otherwise similar reaction conditions (Scheme 1). In order to assess the efficiency and general utility of NfN 3 as an advantageous and safer alternative to TfN 3 for the preparation of organic azides, we have now extended this study to a diverse set of amines, including simple alkylamines, aryl-A C H T U N G T R E N N U N G amines, amino acids, hexosamines, and complex aminoglycosides.…”

Section: Introductionmentioning

confidence: 82%

“…[12] We hoped that the mild conditions of the diazo transfer process would prevent nucleophile-induced cage rearrangements [13] that were expected to occur in alternative routes to 2 using nucleophilic substitution reactions with azide anion. [14] Compound 1, containing eight amino groups, provided a stringent test for the efficiency of the diazo transfer process.…”

Section: Introductionmentioning

confidence: 99%

Nonafluorobutanesulfonyl Azide: A Shelf‐Stable Diazo Transfer Reagent for the Synthesis of Azides from Primary Amines

et al. 2010

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Nonafluorobutanesulfonyl azide is an efficient, shelf-stable and cost-effective diazo transfer reagent for the synthesis of azides from primary amines. The reagent can also be successfully applied to the one-pot regioselective synthesis of 1,2,3-tri-A C H T U N G T R E N N U N G azoles from primary amines by a sequential diazo transfer and azide-alkyne 1,3-dipolar cycloaddition process catalyzed by copper. The cycloaddition step can be conducted in an inter-or intramolecular way to afford 1,4-or 1,5-disubstituted triazoles, respectively. The atypical 1,5-regioselectivity under copper catalysis is a consequence of geometrical constraints of the amino-alkyne substrates used in the intramolecular version. Nonafluorobutanesulfonyl azide offers an advantageous alternative to the better known and most commonly used trifluoromethanesulfonyl azide.

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“…1) and its reaction with a variety of alkynes. [25][26][27][28][29][30][31][32][33][34][35][36] The preparation of octa(3-azidopropyl)polyhedral oligomeric silsesquioxane POSS-(N 3 ) 8 requires a multi-step synthesis and suffers from a poor overall yield of 30-32%.…”

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confidence: 99%

“…The completion of the cycloaddition reaction was conrmed by MALDI-TOF and the reaction progress was monitored by Trastoy et al 32 have reported an efficient preparation of highly functionalised cubic-octameric POSS frameworks by click chemistry and the highest yield (96%) was obtained with the CuSO 4 $H 2 O/sodium ascorbate precatalyst system 20 using a biphasic organic solvent/water mixture at room temperature for 24 hours. We have used these reaction conditions for the functionalisation of the octa-alkyne-terminated POSS with azido-N-Fmoc-norleucine and 3 0 -azido-3 0 -deoxythymidine (Scheme 2).…”

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confidence: 99%

Facile synthesis of novel hybrid POSS biomolecules via “Click” reactions

et al. 2017

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A novel alkyne-terminated cubic-octameric POSS was synthesised in high yield (82-90%). The X-ray crystal structure revealed intra-and intermolecular hydrogen bonding between the amide groups of the arms.Hybrid biomaterials were synthesised in nearly quantitative yields via a click reaction with (i) azido-NFmoc-norleucine and (ii) 3 0 -azido-3 0 -deoxythymidine.Among the most commonly studied scaffolds for developing hybrid biomaterials 1-4 is polyhedral oligomeric silsesquioxane (POSS). POSS units are symmetrical, three-dimensional cubic molecules, which are unique nanometer-sized hybrid inorganicorganic materials 5,6 with the formula ( 'click' chemistry, is a simple method for coupling organic molecules containing azide and alkyne functional groups in high yields and its use in the elds of peptide and protein biomedical and material sciences is accelerating.22,23 The click reaction has been used to synthesise POSS biomaterials such as hybrid POSS-PEG hydrogels 24 that support chondrocyte attachment and proliferation. Only one synthetic approach towards peptidyl silsesquioxanes using click chemistry has been reported to date.25-30 focussing on the synthesis of octa(3-azidopropyl)polyhedral oligomeric silsesquioxane POSS-(N 3 ) 8 (Fig. 1) and its reaction with a variety of alkynes.25-36 The preparation of octa(3-azidopropyl)polyhedral oligomeric silsesquioxane POSS-(N 3 ) 8 requires a multi-step synthesis and suffers from a poor overall yield of 30-32%. 32The synthesis and click reaction of mono alkyneheptaisobutyl POSS were rst reported by Müller et al. 37 and Wu et al. 38 Müller et al. 37 have used aminopropylheptaisobutyl polyhedral oligomeric silsesquioxane (POSS) to produce monoalkyne-POSS in three steps and the click coupling occurred between the azido-terminated polystyrenes and alkyne-POSS to afford mono-, di-, and pentafunctional POSS-containing hybrid polystyrenes as star-shaped telechelic POSS-containing hybrid polymers. Wu et al.38 have prepared alkyne-functionalized-POSS in three steps from allyl-heptaisobutyl substituted-POSS and the product was linked to an azido-functionalized elastomer of poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEB-CH 2 N 3 ) via a click coupling reaction to form a novel hybrid copolymer. These approaches focused mostly on the preparation of a hybrid copolymer based on mono-alkyne-heptaisobutyl and azido polystyrene. However, the preparation of octa-alkyne-terminated POSS and their click coupling reactions with azido-biomolecules to produce hybrid biomaterials has not been investigated yet. We believe that this approach will open a wide range of biomedical applications that were not accessible in the past.Herein we report a novel synthetic approach to hybrid biomaterials based on octa-alkyne-terminated POSS and their reaction with (i) azido-N-Fmoc-L-norleucine and (ii) 3 0 -azido-3 0 -deoxythymidine, using the CuAAC reaction. Our approach Fig. 1 Octa(3-azidopropyl)POSS.

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Octakis(3‐azidopropyl)octasilsesquioxane: A Versatile Nanobuilding Block for the Efficient Preparation of Highly Functionalized Cube‐Octameric Polyhedral Oligosilsesquioxane Frameworks Through Click Assembly

Cited by 70 publications

References 98 publications

Click Assembly of Dye‐Functionalized Octasilsesquioxanes for Highly Efficient and Photostable Photonic Systems

Click Assembly of Dye‐Functionalized Octasilsesquioxanes for Highly Efficient and Photostable Photonic Systems

Nonafluorobutanesulfonyl Azide: A Shelf‐Stable Diazo Transfer Reagent for the Synthesis of Azides from Primary Amines

Facile synthesis of novel hybrid POSS biomolecules via “Click” reactions

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