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Polymeric colorants: Statistical copolymers of indigo building blocks with defined structures

Voss, Gundula, Drechsler, Markus, Eller, Steffen, Gradzielski, Michael, Gunzelmann, Daniel, Mondal, Svastik, van, Smaalen Sander and Voertler, Claus S. 2009, Polymeric colorants: Statistical copolymers of indigo building blocks with defined structures, Helvetica chimica acta, vol. 92, no. 12, pp. 2675-2697, doi: 10.1002/hlca.200900123.

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Title Polymeric colorants: Statistical copolymers of indigo building blocks with defined structures
Author(s) Voss, Gundula
Drechsler, Markus
Eller, Steffen
Gradzielski, Michael
Gunzelmann, Daniel
Mondal, Svastik
van, Smaalen Sander
Voertler, Claus S.
Journal name Helvetica chimica acta
Volume number 92
Issue number 12
Start page 2675
End page 2697
Total pages 23
Publisher Wiley
Place of publication London, Eng.
Publication date 2009-12
ISSN 1522-2675
Keyword(s) polymeric colorants
indigo
NMR spectroscopy
small-angle-neutron scattering
transmission-electron microscopy
polymeric aggregates
Summary Statistical copolymers of indigo (1a) and N-acetylindigo (1b) building blocks with defined structures were studied. They belong to the class of polymeric colorants. The polymers consist of 5,5′-connected indigo units with keto structure and N-acetylindigo units with uncommon tautomeric indoxyl/indolone (=1H-indol-3-ol/3H-indol-3-one) structure (see 2a and 2b in Fig. 1). They formed amorphous salts of elongated monomer lengths as compared to monomeric indigo. The polymers were studied by various spectroscopic and physico-chemical methods in solid state and in solution. As shown by small-angle-neutron scattering (SANS) and transmission-electron microscopy (TEM), disk-like polymeric aggregates were present in concentrated solutions (DMSO and aq. NaOH soln.). Their thickness and radii were determined to be ca. 0.4 and ca. 80 nm, respectively. From the disk volumes and by a Guinier analysis, the molecular masses of the aggregates were calculated, which were in good agreement with each other. Defined structural changes of the polymer chains were observed during several-weeks storage in concentrated DMSO solutions. The original keto structure of the unsubstituted indigo building blocks reverted to the more flexible indoxyl/indolone structure. The new polymers were simultaneously stabilized by intermolecular H-bonds to give aggregates, preferentially dimers. Both aggregation and tautomerization were reversible upon dissolution. The polymers were synthesized by repeated oxidative coupling of 1,1′-diacetyl-3,3′-dihydroxybis-indoles 5 (from 1,1′-diacetyl-3,3′-bis(acetyloxy)bis-indoles 6) followed by gradual hydrolysis of the primarily formed poly(N,N′-diacetylindigos) 7 (Scheme). N,N′-Diacetylbis-anthranilic acids 9 were isolated as by-products.
Language eng
DOI 10.1002/hlca.200900123
Field of Research 039999 Chemical Sciences not elsewhere classified
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1.1 Refereed article in a scholarly journal
Free to Read? Yes
Persistent URL http://hdl.handle.net/10536/DRO/DU:30064440

Document type: Journal Article
Collections: Institute for Frontier Materials
Open Access Collection
GTP Research
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Every reasonable effort has been made to ensure that permission has been obtained for items included in DRO. If you believe that your rights have been infringed by this repository, please contact drosupport@deakin.edu.au.