A facile protection–deprotection route for obtaining indigo pigments as thin films and their applications in organic bulk heterojunctions

Głowacki, Eric Daniel; Voß, Gundula; Demirak, Kadir; Havlíček, Marek; Sünger, Nevsal; Okur, Aysu Ceren; Monkowius, Uwe; Gąsiorowski, Jacek; Leonat, Lucia; Sariciftci, Niyazi Serdar

doi:10.1039/c3cc42889c

Cited by 69 publications

(73 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The initial mass loss for 3c, however, is not consistent with the simple loss of alkyl groups and is likely coupled to halogen removal. The decomposition temperature of 3b agrees favorably to the deprotection of t-Boc units in indigo-based molecules as previously reported [8]. This thermal process was also characterized with UV-Vis spectroscopy.…”

Section: Thermal and Electronic Analysissupporting

confidence: 76%

“…In the case of Boc-protected materials, thermal treatment yields the deprotected material and gaseous products of CO 2 and isobutene as reported previously for diketopyrrolopyrrole-based compounds [6,7]. Very recently Boc-protected indigo dyes have been communicated and these materials allow for solution-processing of indigo films via simple heat treatment [8]. We now report the application of this chemistry to isoindigo dyes and outline the synthesis, crystallographic characterization and physical properties of a Boc-substituted isoindigo and compare its properties to that of an alkyl-substituted isoindigo.…”

Section: Introductionmentioning

confidence: 81%

See 1 more Smart Citation

Synthesis, characterization, and electronic properties of a thermally-labile isoindigo

Pappenfus

Bashir

Gerold

et al. 2015

Journal of Molecular Structure

View full text Add to dashboard Cite

Section: Thermal and Electronic Analysissupporting

confidence: 76%

Section: Introductionmentioning

confidence: 81%

Synthesis, characterization, and electronic properties of a thermally-labile isoindigo

Pappenfus

Bashir

Gerold

et al. 2015

Journal of Molecular Structure

View full text Add to dashboard Cite

“…This procedure was introduced for insoluble industrial pigments like diketopyrrolopyrroles and quinacridones by researchers at the Ciba-Geigy company. [ 16,17 ] Contrary to other H-bonded pigments, which can readily be functionalized with tBOC according to several simple procedures, [16][17][18] the t-butoxycarbonylation of Epi proved to be quite a demanding task. After several attempts, we were able to fi nd the best protocol ( Scheme 2 ) in terms of yields and reaction time.…”

Section: Solubilization Of Epindolidione By T -Butoxycarbonylation (Tmentioning

confidence: 99%

Epindolidiones—Versatile and Stable Hydrogen‐Bonded Pigments for Organic Field‐Effect Transistors and Light‐Emitting Diodes

Głowacki

Romanazzi

Yumusak

et al. 2014

Adv Funct Materials

Self Cite

View full text Add to dashboard Cite

1wileyonlinelibrary.com IntroductionHydrogen-bonded organic pigments are a class of materials familiar from applications in the colorant industry, where they fi nd widespread use as materials for robust outdoor paints, cosmetics, and printing inks. [ 1,2 ] Indigo, a natural product, is the oldest and still most widely produced organic dye and pigment ( Figure 1 ). [ 3 ] The intermolecular -NH … O = hydrogen bonding that characterizes indigo is exploited in most of the synthetic hydrogen-bonded pigments as well. This class of materials has proven to be nontoxic and safe for humans, and is considered safer than even several classes of food dyes. [ 4 ] Hydrogen-bonding as a supramolecular engineering tool is useful to control self-assembly and highly relevant to aqueous and biochemical systems. [ 5,6 ] Recently, we have found that indigo, [ 7 ] and some of its derivatives [ 8,9 ] demonstrate ambipolar transport in organic fi eldeffect transistors (OFETs), with mobility ranging from 0.01-0.4 cm 2 V -1 s -1 . We Epindolidiones-Versatile and Stable Hydrogen-Bonded Pigments for Organic Field-Effect Transistors and Light-Emitting DiodesEric Daniel Głowacki , * Giuseppe Romanazzi , Cigdem Yumusak , Halime Coskun , Uwe Monkowius , Gundula Voss , Max Burian , Rainer T. Lechner , Nicola Demitri , Günther J. Redhammer , Nevsal Sünger , Gian Paolo Suranna and Serdar Sariciftci Hydrogen-bonded pigments are remarkably stable high-crystal lattice energy organic solids. Here a lesser-known family of compounds, the epindolidiones, which demonstrates electronic transport with extraordinary stability, even in highly demanding aqueous environments, is reported. Hole mobilities in the range 0.05-1 cm 2 V -1 s -1 can be achieved, with lower electron mobilities of up to 0.1 cm 2 V -1 s -1 . To help understand charge transport in epindolidiones, X-ray diffraction is used to solve the crystal structure of 2,8-difl uoroepindolidione and 2,8-dichloroepindolidione. Both derivatives crystallize with a linear-chain H-bonding lattice featuring two-dimensional π-π stacking. Powder diffraction indicates that the unsubstituted epindolidione has very similar crystallinity. All types of epindolidiones measured here display strong low-energy optical emission originating from excimeric states, which coexists with higher-energy fl uorescence. This can be exploited in light-emitting diodes, which show the same hybrid singlet and low-energy excimer electroluminescence. Low-voltage FETs are fabricated with epindolidione, which operate reliably under repeated cyclic tests in different ionic solutions within the pH range 3-10 without degradation. Finally, in order to overcome the insolubility of epindolidiones in organic solvents, a chemical procedure is devised to allow solution-processing via the introduction of suitable thermolabile solubilizing groups. This work shows the versatile potential of epindolidione pigments for electronics applications.

show abstract

“…This particular label was chosen because of the photoluminescence peak at 705 nm, which is sufficiently bathochromic of the absorbance of QNC and EPI and therefore could be selectively excited at wavelengths (> 640 nm) where the pigment semiconductors do not absorb and energy transfer and quenching effects can be excluded. 37 Ultrasonication to increase reactivity was also attempted. As shown in Figure 11a, only B7-modified samples showed luminescence from the qdot705 probe following a single washing with PBS solution.…”

Section: Bioconjugation Of Streptavidin With Biotinmentioning

confidence: 99%

Bioconjugation of hydrogen-bonded organic semiconductors with functional proteins

et al. 2015

View full text Add to dashboard Cite

We demonstrate the direct bioconjugation of hydrogen-bonded organic semiconductors with two different complex functional proteins in an aqueous environment. The representative semiconductors are epindolidione and quinacridone, materials used in devices in the form of vacuum-evaporated polycrystalline films. First, these molecules in thin films react spontaneously with N-hydroxysuccinimide functionalized linkers: disuccinimidyl suberate and succinimidyl biotinate. The suberate linker is then used to covalently bind the Rhodobacter sphaeroides reaction centre (RC), the key photoenzyme for conversion of light into electrical charges in photosynthetic bacteria. Similarly, the biotin linker is used to bridge streptavidin to the surface of the hydrogen-bonded semiconductor film. Multiple-reflection infrared spectroscopy, water contact angle measurements, and atomic force microscopy are used to verify surface functionalization. The presence and functional integrity of the immobilized proteins are demonstrated by specific experiments: a charge recombination kinetics assay in the case of the RC, and photoluminescence measurements for quantum dot-labelled streptavidin. As key results of our work, we have shown that upon bioconjugation, the semiconductors preserve their favourable electrical properties: as evidenced by photoconductor devices operating under water sensitized by the RC, and thin film transistor measurements before and after bioconjugation. These are enabling steps for using hydrogen-bonded semiconductors as platforms for multifunctional bioelectronics devices

show abstract

A facile protection–deprotection route for obtaining indigo pigments as thin films and their applications in organic bulk heterojunctions

Cited by 69 publications

References 21 publications

Synthesis, characterization, and electronic properties of a thermally-labile isoindigo

Synthesis, characterization, and electronic properties of a thermally-labile isoindigo

Epindolidiones—Versatile and Stable Hydrogen‐Bonded Pigments for Organic Field‐Effect Transistors and Light‐Emitting Diodes

Bioconjugation of hydrogen-bonded organic semiconductors with functional proteins

Contact Info

Product

Resources

About