Inorganic and organometallic polymers

Rivard, Eric

doi:10.1039/c1ic90002a

Cited by 4 publications

(4 citation statements)

References 123 publications

(134 reference statements)

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“…41–50 Inorganic functional groups are interesting targets for polymer synthesis because they can be expected to have new reactivities that differ from those of organic functional groups and they have the potential to act as ligands for metals. 51–54 The use of inorganic functional group transformations in the synthesis of polymers is understudied and represents a potentially rich source of functional group diversity in macromolecular science.…”

Section: Introductionmentioning

confidence: 99%

“…Most inorganic functional groups found in monomers or polymers are not transformed during the polymerization reaction. Three notable examples of inorganic functional groups that have been polymerized include the polymerization of thiols into poly(disulfides), the polymerization of cyclic phosphazenes into poly(phosphazenes), and the polymerization of cyclic siloxanes into poly(siloxanes). − Inorganic functional groups are interesting targets for polymer synthesis because they can be expected to have new reactivities that differ from those of organic functional groups and they have the potential to act as ligands for metals. − The use of inorganic functional group transformations in the synthesis of polymers is understudied and represents a potentially rich source of functional group diversity in macromolecular science.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of the First Poly(diaminosulfide)s and an Investigation of Their Applications as Drug Delivery Vehicles

et al. 2012

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This paper reports the first examples of poly(diaminosulfide)s that were synthesized by the reaction of a sulfur transfer reagent and several secondary diamines. The diaminosulfide group has the general structure of R2N-S-NR2 and, although it has been used in the synthesis of small molecules, it has never been utilized in the synthesis of macromolecules until this report. A series of poly(diaminosulfide)s were synthesized at elevated temperatures, and the molecular weights of the polymers were as high as 12,400 g mol−1 with conversions for the polymerization reaction up to 99%. The rate constants for the transamination reactions that lead to the polymers were measured in several solvents to provide an understanding the reaction conditions necessary to polymerize the monomers. The degradation of diaminosulfides were studied in D2O, C6D6, CD3OD, CDCl3, and DMSO-d6/D2O to demonstrate that they were very stable in organic solvents but degraded within hours under aqueous conditions. These results clearly demonstrated that diaminosulfides are very stable in organic solvents under ambient conditions. Poly(diaminosulfide)s have sufficient stabilities to be useful for many applications. The ability of these polymers to function as drug delivery vehicles were studied by the fabrication of nanoparticles of a water-insoluble poly(diaminosulfide) with a dye. The microparticles were readily absorbed into human embryonic 293 cells and possessed no measureable toxicity towards these same cells.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of the First Poly(diaminosulfide)s and an Investigation of Their Applications as Drug Delivery Vehicles

et al. 2012

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“…This review article adopts a similar organisational structure to the previous Annual Report in this series. 1 After this Introduction, an overview of the recent books and review articles in the domain of inorganic and organometallic polymers will be given. The proceeding three sections will be focused on research advances within the well-established inorganic polymer classes: polysiloxanes (silicones), polysilanes and their heavier element congeners, and polyphosphazenes.…”

Section: Introductionmentioning

confidence: 99%

Inorganic and organometallic polymers

Rivard

2012

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This article provides an overview of research selected from the 2011 scientific literature involving polymers with inorganic elements as part of their backbone. HighlightsParticularly impressive breakthroughs from the area of inorganic and organometallic polymers include: the synthesis of an inverted bulk heterojunction (BHJ) solar cell featuring dithenylgermoles with an efficiency of 7.3%, 56 the discovery of a photocatalytic route to polyaminoboranes, 62 the controlled preparation of luminescent conjugated organoborane oligomers and the detailed evaluation of their opticoelectronic properties, 65 and the discovery of a reversible cross-linking reaction involving polyisoprene (PI) segments within a polyisoprene-polyferrocenylsilane block copolymer.

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“…[222][223][224][225][226][227][228][229][230] These polymers link the monomers through carbon-carbon bonds as shown in Figure A-1c 231 Inorganic functional groups are interesting targets for polymer synthesis because they can be expected to have new reactivities that differ from those of organic functional groups and they have the potential to act as ligands for metals. [232][233][234][235] The use of inorganic functional group transformations in the synthesis of polymers is understudied and represents a potentially rich source of functional group diversity in macromolecular science. was first synthesized in 1953 from S 2 N 2 .…”

Section: Introductionmentioning

confidence: 99%

Poly(disulfidediamines)

Graf¹

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The turnovers of a gold(III) chloride catalyst were increased by 3,300% with the addition of several equivalents of (2,2,6,6-tretramethyl-piperidin-1-yl)oxy and catalytic amounts of copper(II) chloride. A three component coupling reaction between piperidine, phenylacetylene, and benzaldehyde yielded a propargylamine in quantitative conversions and isolated yields when gold(III) chloride was added in catalytic amounts, but the gold catalyst decomposed and had little to no reactivity when a second set of piperidine, phenylacetylene, and benzaldehyde were added after the reaction was complete. The addition of (2,2,6,6-tretramethyl-piperidin-1-yl)oxy and copper(II) chloride to reactions with gold(III) chloride maintained the catalytic activity of the gold for up to 33 cycles. This result demonstrates a new way to greatly increase the turnovers of a gold(III) chloride catalyst with the addition of inexpensive, commercially available reagents. The synthesis and some of the physical properties of the first poly(disulfidediamines) are reported. These polymers were synthesized in high yields and with conversions up to >98% by reactions between secondary diamines and a new disulfide monomer. The disulfide monomer was synthesized in two steps without the need for column chromatography. The polymerizations were robust and completed at room temperature, under ambient atmospheric conditions, and in solvents that were used as purchased. These polymers were stable, but they rapidly decomposed under acidic, aqueous conditions to release hydrogen sulfide. A method for quantifying the hydrogen sulfide released was also developed.

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Inorganic and organometallic polymers

Cited by 4 publications

References 123 publications

Synthesis of the First Poly(diaminosulfide)s and an Investigation of Their Applications as Drug Delivery Vehicles

Synthesis of the First Poly(diaminosulfide)s and an Investigation of Their Applications as Drug Delivery Vehicles

Inorganic and organometallic polymers

Poly(disulfidediamines)

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