Chemistry and Properties of Indolocarbazoles

Janosik, Tomasz; Rannug, Agneta; Rannug, Ulf; Wahlström, Niklas; Slätt, Johnny; Bergman, Jan

doi:10.1021/acs.chemrev.8b00186

Cited by 134 publications

(90 citation statements)

References 535 publications

(1,143 reference statements)

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“…Photophysical properties of 139a-d 169. ]helicene 142 (Scheme 36) incorporating a diazabenzo ring core165 was successfully synthesized by Ryo Irie et al by a catalytic domino cyclodehydrogenation using Pd(OAc) 2 and O 2 as the key step…”

mentioning

confidence: 99%

Enantioenriched Helicenes and Helicenoids Containing Main-Group Elements (B, Si, N, P)

2019

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In this review, we discuss the rich chemistry of helicenes and helicenoids containing maingroup elements. Enantioenriched helicenic derivatives containing main-group elements B, Si, N and P, either incorporated within the helical backbone or grafted to it, will be thoroughly presented. We will describe their synthesis, resolution, and asymmetric synthesis, their structural features, electronic and chiroptical properties, emission, together with other photochemical properties and applications. OUTLINE 14 The absorption spectrum of 19c recorded in CH 2 Cl 2 solutions exhibited a maximum at 376 nm which is significantly red shifted compared with that of double [5]helicene 19a (310 nm) due to the more extended π-conjugation in 19c. According to TD-DFT calculations, the low-energy absorption band from 400 to 500 nm is assignable to the HOMO→LUMO transition corresponding to a π−π* transition of the fully conjugated bis-helical system. DFT calculations revealed a very high theoretical isomerization barrier of 45.1 kcal/mol for the (P,P)/(M,M)-19c stereoisomer, i.e. 4.4 kcal/mol higher than the (P,M) stereoisomer (not observed experimentally). The high configurational stability of 19c enabled to obtain the pure (P,P)and (M,M)-19c by chiral HPLC (Daicel Chiralcel IE column; EtOAc/MeOH = 9:1 as eluent) and to study their chiroptical properties. The ECD spectrum of (P,P)-19c in CH 2 Cl 2 displayed two strong positive bands at 275 and 320 nm, a strong negative one at 375 nm and a broad and less intense one between 425-475 nm. 52 Note that the isomerization barrier of the OBO-fused double [7]helicene is much higher than for oxabora[6]helicene 9 (vide supra) and higher than carbo[7]helicene (42.0 kcal/ mol), indicating the advantage of double helicenes over monohelicenes in terms of conformational stability. Indeed no racemization was observed upon heating enantiomer (P,P) and (M,M)-19c for 24 h up to 200 °C. 52 Note that in 2017 a longer double OBO-helicene analogue was deposited on a Au(111) under UHV conditions and its surface-assisted cyclodehydrogenation into a planar OBO-perihexacene was observed by STM. 54 Similarly to 6 and 9, the strong bond alternation found in the BOC4 rings of 19a 51 may account for the small NICS value of 1.3 while the surrounding C6 rings, including the distorted central benzene ring, show large negative NICS values (Scheme 3c). For comparison, in the all-carbon analogue tetrabenzo-[a,f,j,o]perylene shown in Scheme 3c, the central C6 ring shows a positive NICS value, indicating substantial antiaromatic character. Notably, molecular orbital calculations of 19a indicate that the HOMO and LUMO are spread over the C6 rings rather than on the boron and oxygen atoms, accounting for the substantial stability of 19a (Scheme 3c). Borahelicenes are efficient blue fluorophores. Indeed, azabora[6]helicene 6 displays blue fluorescence at 447 nm (Table 2), while smaller achiral [4]helicenic systems were successfully used as host materials in phosphorescent OLEDs with efficiencies better than the classical 4,4'...

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confidence: 99%

Enantioenriched Helicenes and Helicenoids Containing Main-Group Elements (B, Si, N, P)

2019

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“…The boron atom in 5 becomes more distorted as compared to 3 a with tetrahedral bond angles ranging from 102.9 to 116.0°and typical values of 104.4 (5)°for NÀ BÀ N and 106.8(5)°f or OÀ BÀ O. As in the previous dyes, the BÀ N bond is slightly longer in the imine (1.572(11) Å) than in the indolocarbazole (1.537 (10) Figure 3, right). Due to this H bonding interaction, molecules are assembled parallelly to make columns and all the columns are arranged in zig-zag manner (Figure 4).…”

Section: X-ray Crystallographymentioning

confidence: 56%

“…Despite of recent advances, examples of the incorporation of boron atoms into 5,11-dihydroindolo[3,2-b]carbazole (ICZs, A, Scheme 1) molecular frame remain rare. [9] ICZs [10] have found widespread use in a large array of applications such as sensing, [11] biological applications, [12] organic field effect transistors (OFETs), [13] organic light emitting diodes (OLEDs), [14] Dye Sensitised Solar Cells (DSSCs) [15] and even in Organic Photovoltaics (OPVs). [16] The high charge carrier mobilities, the possibility to easily tune their electronic levels and their good stability towards atmospheric conditions make them ideal components for use in organic electronics.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Emission Color of Indolo[3,2‐b]carbazole‐Based Boron Complexes and their Application in Organic Field Effect Transistors and Bioimaging

et al. 2020

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Synthetic strategies were developed for the preparation of indolo‐imine boron difluoride (IIBD) dyes based on indolo[3,2‐b]carbazole structures. Four new IIBD dyes were synthesized and were subsequently converted into the corresponding ‐BPh2/‐BOR2 and N‐t‐Boc/N‐benzoyl derivatives. The photophysical properties of all dyes were determined in both solution and solid media. All dyes absorb in the UV/Vis region, show negative solvatochromism, and are fluorescent in both media. The absorbance and fluorescence properties of the dyes can be tuned over a wide range by synthetic modifications. These findings are rationalized by theoretical calculations that correspond well to the experimental shifts, explain the negative solvatochromism, and allow quantification of charge transfer (CT). Similarly, the HOMO–LUMO energies measured by CV are in good agreement with the theoretically calculated values. Interestingly, the energy gaps of the dyes can also be tuned by structural modulations using the developed chemical route. Charge transport properties of the dyes were checked and showed that the N‐benzoyl derivative has the highest hole mobility which is useful for organic field effect transistor (OFET) applications. In addition, easy cellular uptake of the dyes, their low toxicity and high stability inside the cells associated with bright fluorescence in the cytoplasm will be useful for their future application as cellular imaging agents. All of these aspects highlight the interest of this new class of dyes.

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“…After the incubation period, the treatments were terminated by removing the medium and rinsing the cells with phosphate‐buffered saline (PBS). The cells were exposed to the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide dye for 4 hours and the blue‐purple formazan crystal products were dissolved in DMSO for quantification by measuring the absorption at 570 nm …”

Section: Methodsmentioning

confidence: 99%

“…Among all the aryl hydrocarbon receptor (AhR) activators, a signal substance and high‐affinity natural compound, 6‐formyl indolo[3,2‐b]carbazole (FICZ) demonstrates high affinity for the binding and activation of the receptor, and is formed from tryptophan amino acid after exposure to visible/invisible light or via a light‐independent mechanism . FICZ has been shown to play an important role in several physiological pathways, such as the modulation of the immune system, regulation of circadian rhythms, and skin homeostasis . In addition, FICZ in a regulatory feedback mechanism, which can be efficiently metabolized by the cytochrome P450 family 1 enzymes, especially CYP1A1, CYP1A2, and CYP1B1 .…”

Section: Introductionmentioning

confidence: 99%

Aryl hydrocarbon‐estrogen alpha receptor‐dependent expression of miR‐206, miR‐27b, and miR‐133a suppress cell proliferation and migration in MCF‐7 cells

Mobini

Tamaddon

Fardid

et al. 2019

J Biochem & Molecular Tox

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The underlying functions of miR‐206, miR‐133a, miR‐27b, and miR‐21, and their link to the estrogen receptor alpha (ERα) and aryl hydrocarbon receptor (AhR) signaling pathways remain largely unexplored. In this study, we detect the expression of miR‐206, miR‐133a, miR‐27b, and miR‐21 in MCF‐7 through quantificational real‐time polymerase chain reaction assay along with the activation/inhibition of ERα and AhR receptors. Aside from this, cell proliferation and migration as well as AhR‐dependent CYP1A1 enzyme activity were measured. Here, we found that the forced increased expression of miR‐206, miR‐133a, and miR‐27b were closely associated with the suppression of MCF‐7 cell proliferation and migration. The anti‐proliferative‐metastatic effect of miR‐206, miR‐133a, and miR‐27b was probably mediated by targeting the ERα and AhR signaling pathways. Considered together, our study indicated that the overexpression of miR‐206, miR‐133a, and miR‐27b might be potential biomarkers for prognosis and therapeutic strategies in breast cancer.

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Chemistry and Properties of Indolocarbazoles

Cited by 134 publications

References 535 publications

Enantioenriched Helicenes and Helicenoids Containing Main-Group Elements (B, Si, N, P)

Enantioenriched Helicenes and Helicenoids Containing Main-Group Elements (B, Si, N, P)

Tuning the Emission Color of Indolo[3,2‐b]carbazole‐Based Boron Complexes and their Application in Organic Field Effect Transistors and Bioimaging

Aryl hydrocarbon‐estrogen alpha receptor‐dependent expression of miR‐206, miR‐27b, and miR‐133a suppress cell proliferation and migration in MCF‐7 cells

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