Polyisocyanides: Stiffened Foldamers

Otten, Matthijs B. J.; Metselaar, Gerald A.; Cornelissen, Jeroen J. L. M.; Rowan, Alan E.; Nolte, Roeland J. M.

doi:10.1002/9783527611478.ch12

Cited by 5 publications

(2 citation statements)

References 122 publications

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“…Polyisocyanides form a well-known class of static helical polymers [24,25]. They consist of poly(imine) chains in which every carbon atom of the backbone bears a substituent, resulting in an extremely dense comb-like architecture; helical folding of the backbone permits the minimization of steric repulsion between the pendant side groups [26][27][28][29][30]. The introduction of peptide-containing side chains further leads to materials with unprecedented stiffness [31,32].…”

Section: Introductionmentioning

confidence: 99%

Preparation and characterization of non-linear poly(ethylene glycol) analogs from oligo(ethylene glycol) functionalized polyisocyanopeptides

Koepf

Kitto

Schwartz

et al. 2013

European Polymer Journal

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Section: Introductionmentioning

confidence: 99%

Preparation and characterization of non-linear poly(ethylene glycol) analogs from oligo(ethylene glycol) functionalized polyisocyanopeptides

Koepf

Kitto

Schwartz

et al. 2013

European Polymer Journal

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“…Isocyanides have long proven to be valuable compounds in a variety of different fields, such as organic, inorganic, and coordination chemistry. In organic chemistry, they have been widely used as building blocks in the Ugi and Passerini multicomponent reactions and a broad range of other insertion and condensation reactions, including polymerization to polyisocyanides that possess a helical main chain . Furthermore, as stable carbenes that are isoelectronic to CO, they can serve as strong ligands to transitions metals that behave as good σ-donors but are weaker π-acceptors than CO.…”

Section: Introductionmentioning

confidence: 99%

Electronic Properties and Solid-State Packing of Isocyanofulvenes and Their Gold(I) Chloride Complexes

et al. 2020

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Two methods for the synthesis of isocyanofulvenes are reported, and a series of ligands of the type R 5-dibenzo[a,d]cycloheptenylidene; f, 9-thioxanthenylidene; and g, 2,5-dimethyl-3,4-diphenylcyclopentadienylidene) were prepared along with their gold(I) chloride complexes (R 2 CHNC AuCl, 5a−f). A comprehensive study of the properties of the precursors, free ligands, and gold(I) complexes is reported and complemented by DFT calculations. Solid-state structure of two complexes (5a and 5c) show extensive aurophilic interactions and π−π stacking of the ligands. The metal centers are not involved in optical transitions. However, metal coordination leads to a consistent bathochromic shift in the absorption spectra, which signifies the effective conjugation between the isocyano group and the π-systems of the ligands. Furthermore, an additional DFT study of carbonyl complexes of the type R 2 CH−NC−M(CO) 5 (M = Cr, Mo, and W; R 2 CHNC = 4a) indicates very effective metal-to-ligand charge transfer when isocyanopentafulvenes are used as ligands.

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Kinetics of Helix‐Handedness Inversion: Folding and Unfolding in Aromatic Amide Oligomers

et al. 2008

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A series of helically folded oligoamides of 8-amino-2-quinoline carboxylic acid possessing 6, 7, 8, 9, 10 or 16 units are prepared following convergent synthetic schemes. The right-handed (P) and the left-handed (M) helical conformers of these oligomers undergo an exchange slow enough to allow their chromatographic separation on a chiral stationary phase. Thus, the M conformer is isolated for each of these oligomers and its slow racemization in hexane/CHCl(3) solutions is monitored at various temperatures using chiral HPLC. The kinetics of racemization at different temperatures in hexane/CHCl(3) (75:25 vol/vol) are fitted to a first order kinetic model to yield the kinetic constant and the Gibbs energy of activation for oligomers having 6, 7, 8, 9, 10 or 16 quinoline units. This energy gives the first quantitative measure of the exceptional stability of the helical conformers of an aromatic amide foldamer with respect to its partly unfolded conformations that occur between an M helix and a P helix. The trend of the Gibbs energy as a function of oligomer length suggests that helix-handedness inversion does not require a complete unfolding of a helical strand and may instead occur through the propagation of a local unfolding separating two segments of opposite handedness.

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Polyisocyanides: Stiffened Foldamers

Cited by 5 publications

References 122 publications

Preparation and characterization of non-linear poly(ethylene glycol) analogs from oligo(ethylene glycol) functionalized polyisocyanopeptides

Preparation and characterization of non-linear poly(ethylene glycol) analogs from oligo(ethylene glycol) functionalized polyisocyanopeptides

Electronic Properties and Solid-State Packing of Isocyanofulvenes and Their Gold(I) Chloride Complexes

Kinetics of Helix‐Handedness Inversion: Folding and Unfolding in Aromatic Amide Oligomers

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