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Search for "polymer" in Full Text gives 585 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Synthesis of indano[60]fullerene thioketone and its application in organic solar cells
- Yong-Chang Zhai,
- Shimon Oiwa,
- Shinobu Aoyagi,
- Shohei Ohno,
- Tsubasa Mikie,
- Jun-Zhuo Wang,
- Hirofumi Amada,
- Koki Yamanaka,
- Kazuhira Miwa,
- Naoyuki Imai,
- Takeshi Igarashi,
- Itaru Osaka and
- Yutaka Matsuo
Beilstein J. Org. Chem. 2024, 20, 1270–1277, doi:10.3762/bjoc.20.109
- crystalline polymer donor PNTz4T [32] was used. Compared with t-Bu-FIDS, t-Bu-FIDO achieved 3.71% PCE with larger JSC and higher VOC. With PNTz4T, t-Bu-FIDS exhibited low performance, with JSC of only 4 mA/cm2. This lower VOC may be attributable to a suboptimal BHJ structure between PNTz4T and t-Bu-FIDS
Graphical Abstract
Figure 1: Characterization data. (a) FTIR spectra of t-Bu-FIDO and t-Bu-FIDS. (b) UV–vis spectra of fullerene...
Figure 2: Single-crystal structure of t-Bu-FIDS. (a) The π–π distance between two molecules. (b) Crystal pack...
Figure 3: Cyclic voltammograms of fullerene derivatives in o-DCB solution containing Bu4N+(CF3SO2)2N− (0.1 M)...
Figure 4: J–V curves of BHJ OPV devices. (a) ITO/ZnO/fullerene:P3HT (1:1, w/w)/PEDOT:PSS/Ag. (b) ITO/ZnO/full...
Competing electrophilic substitution and oxidative polymerization of arylamines with selenium dioxide
- Vishnu Selladurai and
- Selvakumar Karuthapandi
Beilstein J. Org. Chem. 2024, 20, 1221–1235, doi:10.3762/bjoc.20.105
- polymer 1. The polymer was isolated from the reaction after 3 h, and the supernatant was analyzed for other soluble products. The UV–vis spectrum of polymer 1 dispersed in methanol showed two major peaks at ≈271 and ≈561 nm (Figure S1, Supporting Information File 1), corresponding to the π→π* and
- due to N–H stretching of the polymer [43][44]. The peak appearing at around 3000 cm−1 corresponded to the aryl C–H stretching. The peaks observed at 1593 and 1479 cm−1 were associated with C=C and C=N stretching, respectively. The obtained result was further supported by solid-state synthesis of
- relative to NH2. Scheme 3 shows the reaction of o-anisidine with SeO2. Similar to aniline, a large quantity of o-anisidine was transformed into polymer, labelled polymer 2. The UV–vis and FTIR spectra of polymer 2 are shown in Figures S1 and S2, Supporting Information File 1, respectively. The spectral
Graphical Abstract
Scheme 1: Reported synthetic methods for the selenation of aromatic compounds.
Scheme 2: Reaction of selenium dioxide with aniline.
Scheme 3: Reaction of selenium dioxide with o-anisidine.
Scheme 4: Reaction of methyl anthranilate with SeO2.
Scheme 5: Reaction mechanism for the formation of diaryl monoselenides.
Scheme 6: Reaction mechanism for the formation of oxamides.
Scheme 7: Reaction mechanism for the formation of quinone 10.
Figure 1: Molecular structure of 3. Thermal ellipsoids drawn at 50% probability. Selected bond lengths (Å): O...
Figure 2: Molecular structure of 9. Thermal ellipsoids drawn at 50% probability. Selected bond lengths (Å): O...
Figure 3: Molecular structure of 13. Thermal ellipsoids drawn at 50% probability. Selected bond lengths (Å): ...
Figure 4: Molecular structure of 10. Thermal ellipsoids drawn at 50% probability. Selected bond lengths (Å) a...
Figure 5: Molecular structure of 11. Thermal ellipsoids drawn at 50% probability. Selected bond angles (°): C...
Figure 6: Molecular structure of 12. Thermal ellipsoids drawn at 50% probability. Selected bond angles (°): C...
Figure 7: Relative energy levels of arylamines and SeO2.
Figure 8: Computationally optimized structure of aniline (a), o-anisidine (b), and methyl anthranilate (c), w...
Scheme 8: Resonance structures for the delocalization of the nitrogen lone pair into the π-system.
Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer
- Mohd Farhan Ansari,
- Atul Kumar Maurya,
- Abhishek Kumar and
- Saravanakumar Elangovan
Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98
Graphical Abstract
Scheme 1: General scheme of the borrowing hydrogen (BH) or hydrogen auto-transfer (HA) methodology.
Scheme 2: General scheme for C–N bond formation. A) Traditional cross-couplings with alkyl or aryl halides. B...
Figure 1: Manganese pre-catalysts used for the N-alkylation of amines with alcohols.
Scheme 3: Manganese(I)-pincer complex Mn1 used for the N-alkylation of amines with alcohols and methanol.
Scheme 4: N-Methylation of amines with methanol using Mn2.
Scheme 5: C–N-Bond formation with amines and methanol using PN3P-Mn complex Mn3 reported by Sortais et al. [36]. a...
Scheme 6: Base-assisted synthesis of amines and imines with Mn4. Reaction assisted by A) t-BuOK and B) t-BuON...
Scheme 7: Coupling of alcohols and hydrazine via the HB approach reported by Milstein et al. [38]. aReaction time...
Scheme 8: Proposed mechanism for the coupling of alcohols and hydrazine catalyzed by Mn5.
Scheme 9: Phosphine-free manganese catalyst for N-alkylation of amines with alcohols reported by Balaraman an...
Scheme 10: N-Alkylation of sulfonamides with alcohols.
Scheme 11: Mn–NHC catalyst Mn6 applied for the N-alkylation of amines with alcohols. a3 mol % of Mn6 were used....
Scheme 12: N-Alkylation of amines with primary and secondary alcohols. a80 °C, b100 °C.
Scheme 13: Manganese(III)-porphyrin catalyst for synthesis of tertiary amines.
Scheme 14: Proposed mechanism for the alcohol dehydrogenation with Mn(III)-porphyrin complex Mn7.
Scheme 15: N-Methylation of nitroarenes with methanol using catalyst Mn3.
Scheme 16: Mechanism of manganese-catalyzed methylation of nitroarenes using Mn3 as the catalyst.
Scheme 17: Bidentate manganese complex Mn8 applied for the N-alkylation of primary anilines with alcohols. aOn...
Scheme 18: N-Alkylation of amines with alcohols in the presence of manganese salts and triphenylphosphine as t...
Scheme 19: N-Alkylation of diazo compounds with alcohols using catalyst Mn9.
Scheme 20: Proposed mechanism for the amination of alcohols with diazo compounds catalyzed by catalyst Mn9.
Scheme 21: Mn1 complex-catalyzed synthesis of polyethyleneimine from ethylene glycol and ethylenediamine.
Scheme 22: Bis-triazolylidene-manganese complex Mn10 for the N-alkylation of amines with alcohols.
Figure 2: Manganese complexes applied for C-alkylation reactions of ketones with alcohols.
Scheme 23: General scheme for the C–C bond formation with alcohols and ketones.
Scheme 24: Mn1 complex-catalyzed α-alkylation of ketones with primary alcohols.
Scheme 25: Mechanism for the Mn1-catalyzed alkylation of ketones with alcohols.
Scheme 26: Phosphine-free in situ-generated manganese catalyst for the α-alkylation of ketones with primary al...
Scheme 27: Plausible mechanism for the Mn-catalyzed α-alkylation of ketones with alcohols.
Scheme 28: α-Alkylation of esters, ketones, and amides using alcohols catalyzed by Mn11.
Scheme 29: Mono- and dialkylation of methylene ketones with primary alcohols using the Mn(acac)2/1,10-phenanth...
Scheme 30: Methylation of ketones with methanol and deuterated methanol.
Scheme 31: Methylation of ketones and esters with methanol. a50 mol % of t-BuOK were used, bCD3OD was used ins...
Scheme 32: Alkylation of ketones and secondary alcohols with primary alcohols using Mn4.
Scheme 33: Bidentate manganese-NHC complex Mn6 applied for the synthesis of alkylated ketones using alcohols.
Scheme 34: Mn1-catalyzed synthesis of substituted cycloalkanes by coupling diols and secondary alcohols or ket...
Scheme 35: Proposed mechanism for the synthesis of cycloalkanes via BH method.
Scheme 36: Synthesis of various cycloalkanes from methyl ketones and diols catalyze by Mn13. aReaction time wa...
Scheme 37: N,N-Amine–manganese complex (Mn13)-catalyzed alkylation of ketones with alcohols.
Scheme 38: Naphthyridine‑N‑oxide manganese complex Mn14 applied for the alkylation of ketones with alcohols. a...
Scheme 39: Proposed mechanism of the naphthyridine‑N‑oxide manganese complex (Mn14)-catalyzed alkylation of ke...
Scheme 40: α-Methylation of ketones and indoles with methanol using Mn15.
Scheme 41: α-Alkylation of ketones with primary alcohols using Mn16. aNMR yield.
Figure 3: Manganese complexes used for coupling of secondary and primary alcohols.
Scheme 42: Alkylation of secondary alcohols with primary alcohols catalyzed by phosphine-free catalyst Mn17. a...
Scheme 43: PNN-Manganese complex Mn18 for the alkylation of secondary alcohols with primary alcohols.
Scheme 44: Mechanism for the Mn-pincer catalyzed C-alkylation of secondary alcohols with primary alcohols.
Scheme 45: Upgrading of ethanol with methanol for isobutanol production.
Scheme 46: Mn-Pincer catalyst Mn19 applied for the β-methylation of alcohols with methanol. a2.0 mol % of Mn19...
Scheme 47: Functionalized ketones from primary and secondary alcohols catalyzed by Mn20. aMn20 (5 mol %), NaOH...
Scheme 48: Synthesis of γ-disubstituted alcohols and β-disubstituted ketones through Mn9-catalyzed coupling of...
Scheme 49: Proposed mechanism for the Mn9-catalyzed synthesis of γ-disubstituted alcohols and β-disubstituted ...
Scheme 50: Dehydrogenative coupling of ethylene glycol and primary alcohols catalyzed by Mn4.
Scheme 51: Mn18-cataylzed C-alkylation of unactivated esters and amides with alcohols.
Scheme 52: Alkylation of amides and esters using Mn21.
Scheme 53: α-Alkylation of nitriles with primary alcohols using in situ-generated manganese catalyst.
Scheme 54: Proposed mechanism for the α-alkylation of nitriles with primary alcohols.
Scheme 55: Mn9-catalyzed α-alkylation of nitriles with primary alcohols. a1,4-Dioxane was used as solvent, 24 ...
Figure 4: Manganese complexes used for alkylation of heterocyclic compounds.
Scheme 56: Aminomethylation of aromatic compounds with secondary amines and methanol catalyzed by Mn22.
Scheme 57: Regioselective alkylation of indolines with alcohols catalyzed by Mn9. aMn9 (4 mol %), 48 h.
Scheme 58: Proposed mechanism for the C- and N-alkylation of indolines with alcohols.
Scheme 59: C-Alkylation of methyl N-heteroarenes with primary alcohols catalyzed by Mn1. aTime was 60 h.
Scheme 60: C-Alkylation of oxindoles with secondary alcohols.
Scheme 61: Plausible mechanism for the Mn23-catalyzed C-alkylation of oxindoles with secondary alcohols.
Scheme 62: Synthesis of C-3-alkylated products by coupling alcohols with indoles and aminoalcohols.
Scheme 63: C3-Alkylation of indoles using Mn1.
Scheme 64: C-Methylation of indoles with Mn15 and methanol.
Scheme 65: α-Alkylation of 2-oxindoles with primary and secondary alcohols catalyzed by Mn25. aReaction carrie...
Scheme 66: Dehydrogenative alkylation of indolines with Mn1. aMn1 (5.0 mol %) was used.
Scheme 67: Synthesis of bis(indolyl)methane derivatives from indoles and alcohols catalyzed by Mn26. aMn26 (5....
Scheme 68: One-pot synthesis of pyrimidines via BH.
Scheme 69: Synthesis of pyrroles from alcohols and aminoalcohols using Mn4.
Scheme 70: Synthesis of pyrroles via multicomponent reaction catalyzed by Mn12.
Scheme 71: Friedländer quinoline synthesis using an in situ-generated phosphine-free manganese catalyst.
Scheme 72: Quinoline synthesis using bis-N-heterocyclic carbene-manganese catalyst Mn6.
Scheme 73: Quinoline synthesis using manganese(III)-porphyrin catalyst Mn7.
Scheme 74: Manganese-catalyzed tetrahydroquinoline synthesis via borrowing BH.
Scheme 75: Proposed mechanism for the manganese-catalyzed tetrahydroquinoline synthesis.
Scheme 76: Synthesis of C3-alkylated indoles using Mn24.
Scheme 77: Synthesis of C-3-alkylated indoles using Mn1.
Scheme 78: C–C Bond formation by coupling of alcohols and ylides.
Scheme 79: C-Alkylation of fluorene with alcohols catalyzed by Mn24.
Scheme 80: Proposed mechanism for the C-alkylation of fluorene with alcohols catalyzed by Mn24.
Scheme 81: α-Alkylation of sulfones using Mn-PNN catalyst Mn28.
Light on the sustainable preparation of aryl-cored dibromides
- Fabrizio Roncaglia,
- Alberto Ughetti,
- Nicola Porcelli,
- Biagio Anderlini,
- Andrea Severini and
- Luca Rigamonti
Beilstein J. Org. Chem. 2024, 20, 1076–1087, doi:10.3762/bjoc.20.95
- significant importance as reactive building blocks in polymer and materials chemistry. Their preparation primarily relies on established synthetic methods using molecular bromine or N-bromosuccinimide, known for their reliability and effectiveness. However, from a sustainability perspective, these methods
- building blocks for polymer and materials chemists, offering improved sustainability compared to standard methodologies. Experimental General Solvents and reagents were commercial grade and used as received. 1H NMR spectra were acquired with a Bruker Avance 400 spectrometer (Billerica, MA, USA). The
Graphical Abstract
Figure 1: Comparison between the light-initiated radical halogenation of toluene (right), and the Ar-SE bromi...
Figure 2: Toluene halogenation mediated by NBS in absence (left) or exposed to light (right).
Figure 3: Scifinder® reaction hits for the structure “as drawn” (January 2024).
Figure 4: Yields obtained in the preparation of aryl-cored halides.
Synthesis and characterization of water-soluble C60–peptide conjugates
- Yue Ma,
- Lorenzo Persi and
- Yoko Yamakoshi
Beilstein J. Org. Chem. 2024, 20, 777–786, doi:10.3762/bjoc.20.71
- and nonionic polymer, poly(vinylpyrrolidone) (PVP) [25] and applied these to several in vitro biological assays to report DNA photocleavage [26] and related ROS generation [27][28], antimicrobial photoactivity [29], chondrogenesis-promoting activity [30][31], photocytotoxicity [32][33], and GST enzyme
- -soluble C60 and C70 derivatives by covalently attaching biocompatible water-soluble polymers, such as polyethylene glycol (PEG) [37][38] and PVP [39]. Although these C60– and C70–polymer conjugates revealed high water-solubility, it was found that they, especially the PEG conjugates, formed micelle-like
Graphical Abstract
Figure 1: a) Synthesis of C60–oligopeptide conjugates 5a–c and b) synthesis of compound 3. Fulleropyrrolidine...
Figure 2: Structure of C60–oligo-Lys (5a), C60–oligo-Glu (5b), and C60–oligo-Arg (5c) and images of dissolved...
Figure 3: DLS diagrams of C60–peptide conjugates 5a (1 mM, in Milli-Q® water), 5b (1 mM, in Milli-Q® water or...
Figure 4: UV–vis spectra of C60–peptide conjugates 5a and 5b (20 μM in Milli-Q® water for 5a and in pH 9.0 TR...
Figure 5: 1H NMR spectrum of C60–peptide conjugate 5a in D2O (above) and of the precursor monoadduct in CDCl3...
Figure 6: 13C NMR spectrum of C60–peptide conjugate 5a in D2O and of the precursor monoadduct in CDCl3 at 150...
Figure 7: a) X-band ESR spectra of the 4-oxo-TEMP adduct with 1O2 generated by C60–oligo-Lys (5a) and rose be...
Switchable molecular tweezers: design and applications
- Pablo Msellem,
- Maksym Dekthiarenko,
- Nihal Hadj Seyd and
- Guillaume Vives
Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45
Graphical Abstract
Figure 1: Principle of switchable molecular tweezers.
Figure 2: Principle of pH-switchable molecular tweezers 1 [19].
Figure 3: a) pH-Switchable tweezers 2 substituted with alkyl chains as switchable lipids. b) Schematic depict...
Figure 4: Modification of spectral properties of 3 by controlled induction of Pt–Pt interactions.
Figure 5: Conformational switching of di(hydroxyphenyl)pyrimidine-based tweezer 4 upon alkylation or fluoride...
Figure 6: Hydrazone-based pH-responsive tweezers 5 for mesogenic modulation.
Figure 7: pH-Switchable molecular tweezers 6 bearing acridinium moieties.
Figure 8: a) Terpyridine and pyridine-hydrazone-pyridine analogs molecular tweezers and b) extended pyridine ...
Figure 9: Terpyridine-based molecular tweezers with M–salphen arms and their field of application. Figure 9 was adapt...
Figure 10: a) Terpyridine-based molecular tweezers for diphosphate recognition [48]; b) bishelicene chiroptical te...
Figure 11: Terpyridine-based molecular tweezers with allosteric cooperative binding.
Figure 12: Terpyridine-based molecular tweezers presenting closed by default conformation.
Figure 13: Pyridine-pyrimidine-pyridine-based molecular tweezers.
Figure 14: Coordination-responsive molecular tweezers based on nitrogen-containing ligands.
Figure 15: Molecular tweezers exploiting the remote bipyridine or pyridine binding to trigger the conformation...
Figure 16: Bipyridine-based molecular tweezers exploiting the direct s-trans to s-cis-switching for a) anion b...
Figure 17: a) Podand-based molecular tweezers [66,67]. b) Application of tweezers 32 for the catalytic allosteric reg...
Figure 18: Anion-triggered molecular tweezers based on calix[4]pyrrole.
Figure 19: Anion-triggered molecular tweezers.
Figure 20: a) Principle of the weak link approach (WLA) developed by Mirkin and its application to b) symmetri...
Figure 21: Molecular tweezers as allosteric catalyst in asymmetric epoxide opening [80].
Figure 22: Allosteric regulation of catalytic activity in ring-opening polymerization with double tweezers 41.
Figure 23: a) Conformational switching of 42 by intramolecular –S–S– bridge formation. b) Shift of conformatio...
Figure 24: a) Redox-active glycoluril-TTF tweezers 44. b) Mechanism of stepwise oxidation of said tweezers wit...
Figure 25: Mechanism of formation of the mixed-valence dimers of tweezers 45.
Figure 26: Mechanism of carbohydrate liberation upon redox-mediated conformation switching of 46.
Figure 27: a) The encapsulation properties of 47 as well as the DCTNF release process from its host–guest comp...
Figure 28: Redox-active bipyridinium-based tweezers. a) With a ferrocenyl hinge 49, b) with a propyl hinge 50 ...
Figure 29: Redox-active calix[4]arene porphyrin molecular tweezers.
Figure 30: a) Mechanism of the three orthogonal stimuli. b) Cubic scheme showing the eight different states of ...
Figure 31: Redox-controlled molecular gripper based on a diquinone resorcin[4]arene.
Figure 32: a) Shinkai's butterfly tweezers and their different host–guest properties depending on the isomer. ...
Figure 33: Cyclam-tethered tweezers and their different host–guest complexes depending on their configuration.
Figure 34: Azobenzene-based catalytic tweezers.
Figure 35: Photoswitchable PIEZO channel mimic.
Figure 36: Stilbene-based porphyrin tweezers for fullerene recognition.
Figure 37: Stiff-stilbene-based tweezers with urea or thiourea functional units for a) anion binding, b) anion...
Figure 38: Feringa’s photoswitchable organocatalyst (a) and different catalyzed reactions with that system (b)....
Figure 39: a) Irie and Takeshita’s thioindigo-based molecular tweezers. b) Family of hemithioindigo-based mole...
Figure 40: Dithienylethylene crown ether-bearing molecular tweezers reported by Irie and co-workers.
Green and sustainable approaches for the Friedel–Crafts reaction between aldehydes and indoles
- Periklis X. Kolagkis,
- Eirini M. Galathri and
- Christoforos G. Kokotos
Beilstein J. Org. Chem. 2024, 20, 379–426, doi:10.3762/bjoc.20.36
- to the employment of GO–CuBr without overshadowing its applications [113]. Shirini et al. utilized the polymer poly(4-vinylpyridine) (P4VPy) for the immobilization of nanoparticles in lieu of silica, due to the strong affinity of the pyridyl group towards metals and its ability to undergo hydrogen
- . immobilized carbon nanotubes on sulfonated polyacrylamide creating polymer/carbon nanotube composites, which could also be employed in the synthesis of BIMs [115][116]. This methodology used a catalyst loading of 5 mol % under reflux conditions (85 °C) in acetonitrile for 30–40 minutes with product yields
Graphical Abstract
Scheme 1: Examples of BIMs used for their medicinal properties.
Scheme 2: Mechanisms for the synthesis of BIMs using protic or Lewis acids as catalysts.
Scheme 3: Synthesis of bis(indolyl)methanes using DBDMH.
Scheme 4: Competition experiments and synthesis of bis(indolyl)methanes using DBDMH.
Scheme 5: Proposed mechanism for formation of BIM of using DBDMH.
Scheme 6: Synthesis of bis(indolyl)methanes using I2.
Scheme 7: General reaction mechanism upon halogen bonding.
Scheme 8: Synthesis of bis(indolyl)methanes using I2, introduced by Ji.
Scheme 9: Synthesis of bis(indolyl)methanes using Br2 in CH3CN.
Scheme 10: Βidentate halogen-bond donors.
Scheme 11: Synthesis of bis(indolyl)methanes using bidentate halogen-bond donor 26.
Scheme 12: Proposed reaction mechanism.
Scheme 13: Synthesis of bis(indolyl)methanes using iodoalkyne as catalyst.
Scheme 14: Proposed reaction mechanism.
Scheme 15: Optimized reaction conditions used by Ramshini.
Scheme 16: Activation of the carbonyl group by HPA/TPI-Fe3O4.
Scheme 17: Synthesis of BIMs in the presence of nanoAg-Pt/SiO2-doped silicate.
Scheme 18: Mechanism of action proposed by Khalafi-Nezhad et al.
Scheme 19: Activation of the carbonyl group by the Cu–isatin Schiff base complex.
Scheme 20: Optimum reaction conditions published by Jain.
Scheme 21: Organocatalytic protocol utilizing nanoparticles introduced by Bankar.
Scheme 22: Activation of the carbonyl group by the AlCl3·6H2O-SDS-SiO2 complex.
Scheme 23: Optimal reaction conditions for the aforementioned nano-Fe3O4 based catalysts.
Scheme 24: Nanocatalytic protocol proposed by Kaur et al.
Scheme 25: Microwave approach introduced by Yuan.
Scheme 26: Microwave approach introduced by Zahran et al.
Scheme 27: Microwave irradiation protocol introduced by Bindu.
Scheme 28: Silica-supported microwave irradiation protocol.
Scheme 29: Proposed mechanism for formation of BIM by Nongkhlaw.
Scheme 30: Microwave-assisted synthesis of BIMs catalyzed by succinic acid.
Scheme 31: Proposed mechanism of action of MMO-4.
Scheme 32: Catalytic approach introduced by Muhammadpoor-Baltork et al.
Scheme 33: Reaction conditions used by Xiao-Ming.
Scheme 34: Ultrasonic irradiation-based protocol published by Saeednia.
Scheme 35: Pyruvic acid-mediated synthesis of BIMs proposed by Thopate.
Scheme 36: Synthesis of BIMs using [bmim]BF4 or [bmim]PF6 ionic liquids.
Scheme 37: Synthesis of BIMs utilizing In(OTf)3 in octylmethylimidazolium hexafluorophosphate as ionic liquid.
Scheme 38: FeCl3·6H2O-catalyzed synthesis of BIMs with use of ionic liquid.
Scheme 39: Synthesis of BIMs utilizing the [hmim]HSO4/EtOH catalytic system.
Scheme 40: Synthesis of BIMs utilizing acidic ionic liquid immobilized on silica gel (ILIS-SO2Cl).
Scheme 41: The [bmim][MeSO4]-catalyzed reaction of indole with various aldehydes.
Scheme 42: The role of [bmim][MeSO4] in catalyzing the reaction of indole with aldehydes.
Scheme 43: Synthesis of BIMs utilizing FeCl3-based ionic liquid ([BTBAC]Cl-FeCl3) as catalyst.
Scheme 44: Synthesis of BIMs using [Msim]Cl at room temperature.
Scheme 45: [Et3NH][H2PO4]-catalyzed synthesis of bis(indolyl)methanes.
Scheme 46: PILs-catalyzed synthesis of bis(indolyl)methanes.
Scheme 47: FSILs-mediated synthesis of bis(indolyl)methanes.
Scheme 48: Possible “release and catch” catalytic process.
Scheme 49: Synthesis of bis(indolyl)methanes by [DABCO-H][HSO4].
Scheme 50: Synthesis of bis(indolyl)methanes by [(THA)(SO4)].
Scheme 51: Synthesis of BBSI-Cl and BBSI-HSO4.
Scheme 52: Synthesis of BIMs in the presence of BBSI-Cl and BBSI-HSO4.
Scheme 53: Chemoselectivity of the present method.
Scheme 54: Synthesis of BIMs catalyzed by chitosan-supported ionic liquid.
Scheme 55: Proposed mechanism of action of CSIL.
Scheme 56: Optimization of the reaction in DESs.
Scheme 57: Synthesis of BIMs using ChCl/SnCl2 as DES.
Scheme 58: Synthesis of BIMs derivatives in presence of DES.
Scheme 59: BIMs synthesis in choline chloride/urea (CC/U).
Scheme 60: Flow chemistry-based synthesis of BIMs by Ley.
Scheme 61: Flow chemistry-based synthesis of BIMs proposed by Nam et al.
Scheme 62: Amino-catalyzed reaction of indole with propionaldehyde.
Scheme 63: Aminocatalytic synthesis of BIMs.
Scheme 64: Proposed mechanism for the aminocatalytic synthesis of BIMs.
Scheme 65: Enzymatic reaction of indole with aldehydes.
Scheme 66: Proposed mechanism for the synthesis of BIMs catalyzed by TLIM.
Scheme 67: Proposed reaction mechanism by Badsara.
Scheme 68: Mechanism proposed by D’Auria.
Scheme 69: Photoinduced thiourea catalysis.
Scheme 70: Proposed mechanism of photoacid activation.
Scheme 71: Proposed mechanism of action for CF3SO2Na.
Scheme 72: Proposed mechanism for the synthesis of BIMs by Mandawad.
Scheme 73: Proposed mechanism for the (a) acid generation and (b) synthesis of BIMs.
Scheme 74: a) Reaction conditions employed by Khaksar and b) activation of the carbonyl group by HFIP.
Scheme 75: Activation of the carbonyl group by the PPy@CH2Br through the formation of a halogen bond.
Scheme 76: Reaction conditions utilized by Mhaldar et al.
Scheme 77: a) Reaction conditions employed by López and b) activation of the carbonyl group by thiourea.
Scheme 78: Infrared irradiation approach introduced by Luna-Mora and his research group.
Scheme 79: Synthesis of BIMs with the use of the Fe–Zn BMOF.
Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments
- Aissam Okba,
- Pablo Simón Marqués,
- Kyohei Matsuo,
- Naoki Aratani,
- Hiroko Yamada,
- Gwénaël Rapenne and
- Claire Kammerer
Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30
- synthesized thiepine-containing polymers designed to undergo redox-driven bent-to-planar conformational changes [63]. However, upon electrochemical oxidation of the drop-cast film of polymer 13, the authors observed the conversion of the dithienobenzothiepine monomeric units into dithienonaphthalenes, which
Graphical Abstract
Scheme 1: “Precursor approach” for the synthesis of π-conjugated polycyclic compounds, with the thermally- or...
Scheme 2: Valence isomerization of chalcogen heteropines and subsequent cheletropic extrusion in the case of ...
Scheme 3: Early example of phenanthrene synthesis via a chemically-induced S-extrusion (and concomitant decar...
Scheme 4: Top: Conversion of dinaphthothiepine bisimides 3a,b and their sulfoxide analogues 4a,b into PBIs 6a,...
Figure 1: Top view (a) and side view (b) of the X-ray crystal structure of thiepine 3b showing its bent confo...
Scheme 5: Modular synthetic route towards dinaphthothiepines 3a–f and the corresponding S-oxides 4a–d, incorp...
Scheme 6: Top: Conversion of dithienobenzothiepine monomeric units into dithienonaphthalenes, upon S-extrusio...
Scheme 7: Synthesis of S-doped extended triphenylene derivative 22 from 3-bromothiophene (17) with the therma...
Scheme 8: Top: Synthesis of thermally-stable O-doped HBC 26a. Bottom: Synthesis of S- and Se-based soluble pr...
Scheme 9: Synthesis of dinaphthooxepine bisimide 33 and conversion into PBI 6f by O-extrusion triggered by el...
Figure 2: Cyclic voltammogram of dinaphthooxepine 33, evidencing the irreversibility of the reduction process...
Scheme 10: Top: Early example of 6-membered ring contraction with concomitant S-extrusion leading to dinaphtho...
Scheme 11: Examples of S-extrusion from annelated 1,2-dithiins under photoactivation (top) or thermal activati...
Scheme 12: Synthesis of dibenzo[1,4]dithiapentalene upon photoextrusion of SO2 [78].
Scheme 13: Extrusion of SO in naphthotrithiin-2-oxides for the synthesis of 2,5-dihydrothiophene 1-oxides [79].
Scheme 14: SO-extrusion as a key step in the synthesis of fullerenes (C60 and C70) encapsulating H2 molecules [80,82]....
Scheme 15: Synthesis of diepoxytetracene precursor 56 and its on-surface conversion into tetracene upon O-extr...
Scheme 16: Soluble precursors of hexacene, decacene and dodecacene incorporating 1,4-epoxides in their hydroca...
Scheme 17: Synthesis of tetraepoxide 59 as soluble precursor of decacene [85].
Figure 3: Constant-height STM measurement of decacene on Au(111) using a CO-functionalized tip (sample voltag...
Photochromic derivatives of indigo: historical overview of development, challenges and applications
- Gökhan Kaplan,
- Zeynel Seferoğlu and
- Daria V. Berdnikova
Beilstein J. Org. Chem. 2024, 20, 228–242, doi:10.3762/bjoc.20.23
- in the presence of water in organic solvent. In 2023, Huang, Hecht, Priimagi and co-workers provided the first study of the photoswitching of Ν,Ν'-derivatized indigos in polymer films of different rigidity and described the molecular design strategy allowing to improve the photoswitching performance
- within the polymer matrix [67]. Based on the obtained results, the authors are aiming to translate the photoswitching effect to the macroscopic level and to achieve the modulation of macroscopic properties of materials by red light. Conclusion From the first report on the photochromic N,N'-diacetylindigo
Graphical Abstract
Figure 1: Precursors used in the synthesis of indigo [4].
Figure 2: a) Intramolecular (a = 2.26 Å) and intermolecular (b = 2.11 Å) hydrogen bonds in indigo, b) crystal...
Figure 3: Bond length in the indigo molecule obtained from the single crystal X-ray analysis [12], the typical bo...
Figure 4: The structure of the indigo chromophore (H-chromophore, highlighted in blue), asterisk indicates th...
Figure 5: Influence of substituents in the benzene rings on the color of indigo derivatives.
Figure 6: a) E–Z photoisomerization of indigo and b) photoinduced proton transfer in the excited state, aster...
Figure 7: Structures of indigo derivatives discussed in this review.
Figure 8: Photoswitching of N,N'-diacetylindigo (9a) in CCl4 (c = 17.1 µM; cell length = 5.0 cm) irradiated w...
Figure 9: Photoisomerization of compound 18c upon irradiation with red light and schematic representation of ...
Figure 10: Schematic representation of indigo-type (left) and amide-type (right) resonances in N,N'-acetylindi...
Figure 11: Suggested intermediates for the double bond cleavage for the thermal relaxation of N,N'-diacylindig...
Figure 12: Zwitterionic resonance structures of Z-indigo.
Figure 13: Photos of crystalline N,N'-di(Boc)indigo 17a its solutions in 1) DMSO, 2) DMF, 3) N-methyl-2-pyrrol...
Figure 14: Structural isomers of indigo.
Figure 15: Photochromism of indirubin derivatives and supramolecular complexation of the E-isomers with Schrei...
Figure 16: Photoisomerization of the protonated isoindigo.
Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes
- Michio Yamada
Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13
- . This endeavor aims to delineate new directions for prospective applications of push–pull chromophores. Notably, in polymer chemistry, significant progress has been made in employing [2 + 2] CA–RE reactions for polymers as a valuable post-functionalization treatment [9][10]. However, this topic lies
Graphical Abstract
Scheme 1: Pathway of the [2 + 2] CA–RE reaction of an electron-rich alkyne with TCNE or TCNQ. EDG = electron-...
Scheme 2: Reaction pathway for DMA-appended acetylene and TCNEO.
Scheme 3: Pathway of the [2 + 2] CA–RE reaction between 1 and DCFs.
Scheme 4: Sequential double [2 + 2] CA–RE reactions between 1 and TCNE.
Scheme 5: Divergent chemical transformation pathways of TCBD 6.
Scheme 6: Synthesis of 12.
Scheme 7: [2 + 2] CA–RE reaction of 1 with 14. TCE = 1,1,2,2-tetrachloroethane.
Scheme 8: Autocatalytic model proposed by Nielsen et al.
Scheme 9: Synthesis of anthracene-embedded TCBD compound 19.
Scheme 10: Sequence of the [2 + 2] CA–RE reaction between dibenzo-fused cyclooctyne or cyclooctadiyne and TCNE...
Scheme 11: [2 + 2] CA–RE reaction between the CPP derivatives and TCNE. THF = tetrahydrofuran.
Scheme 12: [2 + 2] CA–RE reaction between ethynylfullerenes 31 and TCNE and subsequent thermal rearrangement.
Scheme 13: Pathway of the [2 + 2] CA–RE reaction between TCNE and 34, followed by additional skeletal transfor...
Scheme 14: Synthesis scheme for heterocycle 38 from the reaction between TCNE and 1 in water and a surfactant.
Scheme 15: Synthesis scheme of the CDA product 41.
Scheme 16: Synthesis of rotaxanes 44 and 46 via the [2 + 2] CA–RE reaction.
Scheme 17: Synthesis of a CuI bisphenanthroline-based rotaxane 50.
Figure 1: Structures of the chiral push–pull chromophores 51–56.
Figure 2: Structures of the axially chiral TCBD 57 and DCNQ 58 bearing a C60 core.
Figure 3: Structures of the axially chiral SubPc–TCBD–aniline conjugates 59 and 60 and the subporphyrin–TCBD–...
Figure 4: Structures of 63 and the TCBD 64.
Figure 5: Structures of the fluorophore-containing TCBDs 65–67.
Figure 6: Structures of the fluorophore-containing TCBDs 68–72.
Figure 7: Structures of the urea-containing TCBDs 73–75.
Figure 8: Structures of the fullerene–TCBD and DCNQ conjugates 76–79 and their reference compounds 80–83.
Figure 9: Structures of the ZnPc–TCBD–aniline conjugates 84 and 85.
Figure 10: Structures of the ZnP–PCBD and TCBD conjugates 86–88.
Figure 11: Structures of the porphyrin-based donor–acceptor conjugates (89–104).
Figure 12: Structures of the porphyrin–PTZ or DMA conjugates 105–112.
Figure 13: Structures of the BODIPY–Acceptor–TPA or PTZ conjugates 113–116.
Figure 14: Structures of the corrole–TCBD conjugates 117 and 118.
Figure 15: Structure of the dendritic TCBD 119.
Figure 16: Structures of the TCBDs 120–126.
Figure 17: Structures of the precursor 127 and TCBDs 128–130.
Figure 18: Structures of 131–134 utilized for BHJ OSCs.
Long oligodeoxynucleotides: chemical synthesis, isolation via catching-by-polymerization, verification via sequencing, and gene expression demonstration
- Yipeng Yin,
- Reed Arneson,
- Alexander Apostle,
- Adikari M. D. N. Eriyagama,
- Komal Chillar,
- Emma Burke,
- Martina Jahfetson,
- Yinan Yuan and
- Shiyue Fang
Beilstein J. Org. Chem. 2023, 19, 1957–1965, doi:10.3762/bjoc.19.146
- monomers N,N-dimethylacrylamide and sodium acrylate, and the cross-linking agent N,N'-methylenebisacrylamide were added, and the polymerization was initiated with ammonium persulfate and N,N,N',N'-tetramethylethylenediamine (TMEDA). The full-length sequence 3 was co-polymerized into the polymer 5, and
Graphical Abstract
Figure 1: Workflow for the construction, verification, and expression of the 800 bp GFP gene from chemically ...
Scheme 1: Structure of phosphoramidites 1a,b and 2, and the catching-by-polymerization (CBP) process.
Figure 2: Gel electrophoresis images of 399 bp (A), 401 bp (B), and 800 bp (C) dsODNs derived from synthetic ...
Figure 3: Gel electrophoresis images of ≈399 and ≈401 bp dsODNs originated from synthetic 399 and 401 nt ssOD...
Figure 4: Images of E. coli containing the GFP gene. (A) The GFP gene was derived from the 399 and 401 nt che...
Aromatic systems with two and three pyridine-2,6-dicarbazolyl-3,5-dicarbonitrile fragments as electron-transporting organic semiconductors exhibiting long-lived emissions
- Karolis Leitonas,
- Brigita Vigante,
- Dmytro Volyniuk,
- Audrius Bucinskas,
- Pavels Dimitrijevs,
- Sindija Lapcinska,
- Pavel Arsenyan and
- Juozas Vidas Grazulevicius
Beilstein J. Org. Chem. 2023, 19, 1867–1880, doi:10.3762/bjoc.19.139
- Karolis Leitonas Brigita Vigante Dmytro Volyniuk Audrius Bucinskas Pavels Dimitrijevs Sindija Lapcinska Pavel Arsenyan Juozas Vidas Grazulevicius Department of Polymer Chemistry and Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50254, Kaunas, Lithuania Latvian Institute of
Graphical Abstract
Figure 1: Chemical structures of pyridine-3,5-dicarbonitrile-based TADF emitters.
Scheme 1: Synthesis of dicyanocarbazole 6. Reaction conditions: a) cyanoacetamide, piperidine, methanol, 40 °...
Scheme 2: Synthesis of dicyanocarbazoles 7–9. Reaction conditions: a) corresponding ethynyl arene, Pd(Ph3P)4 ...
Figure 2: Absorption (a, b) and PL (c, d) spectra of dilute toluene, THF, and chloroform solutions (10−5 M) a...
Figure 3: PL spectra (a) and PL decay curves (b) of air-equilibrated (as prepared) and deoxygenated toluene s...
Figure 4: Non-normalized (a) and normalized (b) PL spectra and PL decay curves (c) of the film of a 10 wt % m...
Figure 5: TGA (a) and DSC 2nd heating (b) curves of compounds 6–9.
Figure 6: CV curves of compounds 6–9.
Figure 7: Photoelectron emission spectra of the vacuum-deposited films of compounds 6–9 on glass substrates c...
Figure 8: The current transients (a) for electrons recorded at the different voltages for the vacuum-deposite...
GlAIcomics: a deep neural network classifier for spectroscopy-augmented mass spectrometric glycans data
- Thomas Barillot,
- Baptiste Schindler,
- Baptiste Moge,
- Elisa Fadda,
- Franck Lépine and
- Isabelle Compagnon
Beilstein J. Org. Chem. 2023, 19, 1825–1831, doi:10.3762/bjoc.19.134
- biopolymer have been established decades ago and are commonly used in a routine and automated manner. However, the development of such technology for the sequencing of the third class of biological polymer – glycans, also known as carbohydrates, saccharides, or "sugars" – lags far behind. This lack of
- (position and anomericity). Based on this basic principle, the identification of an unknown carbohydrate proceeds as follows: the polymer is fragmented in monomers, yet maintaining information on the initial structure and the spectroscopic fingerprint (frequency and intensity of the vibrational modes) of
Graphical Abstract
Figure 1: (a) Fingerprint of an unknown monosaccharide. (b) Labelled reference spectra of monosaccharide stan...
Figure 2: Typical experimental MS–IR spectra of the four categories of monosaccharides included in the first ...
Figure 3: Synthetic IRMPD spectrum (grey trace) generated on the basis of a high resolution endogeneous exper...
Figure 4: Model accuracy dependance with experimental conditions, represented by the dataset augmentation par...
Figure 5: DNN Prediction results for third endogenous dataset (5 hexosamine samples and 7 other molecules). T...
Quinoxaline derivatives as attractive electron-transporting materials
- Zeeshan Abid,
- Liaqat Ali,
- Sughra Gulzar,
- Faiza Wahad,
- Raja Shahid Ashraf and
- Christian B. Nielsen
Beilstein J. Org. Chem. 2023, 19, 1694–1712, doi:10.3762/bjoc.19.124
- . Overall, this review presents a first detailed account of the electron transport properties of Qx derivatives in recent times, offering valuable insights into their potential as promising ETMs. Review Quinoxalines as polymer acceptors The development of efficient and high-performing polymer materials
- based on Qxs is of significant interest in the field of organic electronics. A compelling indication of this potential is the remarkable achievements made by a relatively simple polymer, poly[(thiophene)-alt-(6,7-difluoro-2-(2-hexyldecyloxy)quinoxaline)] (PTQ10). PTQ10 has demonstrated impressive power
- conversion efficiencies (PCEs) of over 12% in polymer solar cells (PCS) when paired with the IDT acceptor [15], over 16% with the Y6 acceptor [16][17] and a champion PCE of 21.2% in perovskite solar cells [18]. This outstanding performance is attributed to the versatile and tunable nature of the Qx moiety
Graphical Abstract
Figure 1: Structures of some of the most versatile Qx scaffolds; dashed lines indicate the substitution sites...
Figure 2: Qx-derived polymer acceptors.
Figure 3: Qx-derived small molecule NFAs.
Figure 4: Qx-derived small molecule NFAs.
Figure 5: Dyes and sensitizers based on Qx auxiliary acceptors or bridging units.
Figure 6: Qx-derived n-type transistor materials.
Figure 7: Qx-derived ETM and TADF emitters.
Figure 8: Qx-derived chromophores.
Benzoimidazolium-derived dimeric and hydride n-dopants for organic electron-transport materials: impact of substitution on structures, electrochemistry, and reactivity
- Swagat K. Mohapatra,
- Khaled Al Kurdi,
- Samik Jhulki,
- Georgii Bogdanov,
- John Bacsa,
- Maxwell Conte,
- Tatiana V. Timofeeva,
- Seth R. Marder and
- Stephen Barlow
Beilstein J. Org. Chem. 2023, 19, 1651–1663, doi:10.3762/bjoc.19.121
- ]. V derivatives have also been obtained as pyrolysis products of a variety of Y = aryl 1H derivatives [33], while Vb has also been found to be both a solution decomposition product of 1bH [27][34] and a beneficial additive for a 1bH-doped polymer [27], and has been crystallographically characterized
Graphical Abstract
Figure 1: DMBI+, DMBI-H, and (DMBI)2 derivatives discussed in this work (new compounds in red).
Scheme 1: Synthesis of DMBI-H and (DMBI)2 derivatives and structures of side products.
Figure 2: Crystallographically characterized molecules related to DMBI dimers.
Figure 3: Molecular structures from the single crystal structures of 1b2 (two crystallographically inequivale...
Figure 4: Molecular structures from the single crystal structures of 1bH (upper left), 1gH (upper right), 1hH...
Figure 5: Structures of the cations from the single crystal structures of 1g+I− (left), 1h+PF6− (center), and ...
Figure 6: Cyclic voltammograms (50 mV s−1, THF, 0.1 M Bu4NPF6) of 1g+PF6–, 1gH, and 1g2, in each case contain...
Figure 7: Acceptors used to examine reactivity of DMBI-H and (DMBI)2 derivatives.
Figure 8: a) Temporal evolution of the absorbance at 1030 nm, corresponding to an absorption maximum of VI•–,...
Tying a knot between crown ethers and porphyrins
- Maksym Matviyishyn and
- Bartosz Szyszko
Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120
- . Osuka and co-workers provided novel insight into the meso-appended crown ether porphyrins, namely, chromophore-incorporated and polymer-based systems capable of acting as multitopic receptors for transition, alkali, and alkali-earth metal cations, which were proved as optical sensing agents among other
Graphical Abstract
Figure 1: Porphyrin and crown ether.
Figure 2: Timeline demonstrating the contributions into the crown ether–porphyrin chemistry.
Figure 3: Tetra-crowned porphyrin 1 and dimer 2 formed upon K+ binding.
Figure 4: meso-Crowned 25-oxasmaragdyrins 3a–c and their boron(III) complexes (3a–c)-BF2.
Scheme 1: CsF ion-pair binding of 4. The molecular structure of 4-CsF is shown on the right [101].
Figure 5: CsF ion pair binding by 5. The molecular structure of 5-CsF is shown on the right [102].
Scheme 2: Ion-pair binding by 6. The molecular structure of (6-CsCl)2 is shown on the right [103].
Scheme 3: Hydrated fluoride binding by 7 [104].
Figure 6: β-Crowned porphyrin 8.
Figure 7: Crown ether-capped porphyrins 9.
Figure 8: The capped porphyrin 10 and complex [10-PQ](PF6)2.
Figure 9: The double-capped porphyrin 11.
Figure 10: Selected examples of iminoporphyrinoids [58,122].
Scheme 4: The synthesis of 13.
Scheme 5: Tripyrrane-based crown ether-embedding porphyrinoid 15.
Figure 11: Macrocycles 16–19 and their coordination compounds.
Scheme 6: The flexibility of 16-Co [66].
Figure 12: Hexagonal wheel composed of six 16-Co(III) monomers [66].
Scheme 7: The synthesis of 16-V [67].
Figure 13: The molecular structure of dimers [16-Mn]2 [67].
Scheme 8: Synthesis of crownphyrins 28–33. Compounds 23a/b and 29a/b were obtained from 4,7,10-trioxa-1,13-tr...
Figure 14: The molecular structures of 22a, 34a·(HCl)2, and 29b [69].
Figure 15: Molecular structures of 22a-Pb and (29b)2-Zn [69].
Scheme 9: Reactivity of 29a/b.
Scheme 10: Synthesis of 36 and 37 [131].
Scheme 11: Synthesis of 40–45.
Figure 16: Potential applications of porphyrin-crown ether hybrids.
Radical chemistry in polymer science: an overview and recent advances
- Zixiao Wang,
- Feichen Cui,
- Yang Sui and
- Jiajun Yan
Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116
- Zixiao Wang Feichen Cui Yang Sui Jiajun Yan School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Rd., Shanghai, 201210, China 10.3762/bjoc.19.116 Abstract Radical chemistry is one of the most important methods used in modern polymer science and industry. Over the
- past century, new knowledge on radical chemistry has both promoted and been generated from the emergence of polymer synthesis and modification techniques. In this review, we discuss radical chemistry in polymer science from four interconnected aspects. We begin with radical polymerization, the most
- employed technique for industrial production of polymeric materials, and other polymer synthesis involving a radical process. Post-polymerization modification, including polymer crosslinking and polymer surface modification, is the key process that introduces functionality and practicality to polymeric
Graphical Abstract
Scheme 1: Oxidation of catechol and subsequent cross-linking. Scheme 1 redrawn from [3].
Scheme 2: (A) Structure of typical urushiol in Chinese lacquer, and (B) schematic process of laccase-catalyze...
Scheme 3: A) Primary amino acid sequence of mfp-1, mfp-3, and mfp-5 (Y: DOPA, K: lysine). B) Scheme showing e...
Scheme 4: Activation–deactivation equilibrium in nitroxide-mediated polymerizations. Bicomponent initiating s...
Scheme 5: Mechanism of a transition metal complex-mediated ATRP. Scheme 5 redrawn from [14].
Scheme 6: Mechanism of RAFT polymerization. Scheme 6 redrawn from [68].
Scheme 7: Degenerative transfer (a) and reversible termination (b) mechanism of OMRP. Scheme 7 redrawn from [70].
Scheme 8: Simplified mechanism of a RITP. Scheme 8 redrawn from [21].
Scheme 9: (A) Structures of π-conjugated conductive polymers. (B) Examples of conductive polymer synthesis vi...
Scheme 10: Possible regiochemical couplings in PATs. Scheme 10 redrawn from [79].
Scheme 11: General thiol-ene photopolymerization process. Scheme 11 redrawn from [81].
Scheme 12: (a) Three generations of Grubbs catalysts. (b) Proposed mechanism for photo-ROMP via a reductive qu...
Scheme 13: Pyrylium and thiopyrylium salts studied by Boydston et al. Scheme 13 redrawn from [91].
Scheme 14: A general illustration of post-polymerization modification by thiol–ene chemistry.
Scheme 15: Introduction of functionalities by nitroxide radical coupling of HO-TEMPO derivatives.
Scheme 16: Chemical reaction process scheme of DCP-induced crosslinking of LDPE. Scheme 16 redrawn from [126].
Scheme 17: A probable mechanism of radical-induced hydrosilylation.
Scheme 18: Polymer surface modification by homolytic dediazonation of diazonium salts.
Scheme 19: Photoinduced polymer surface modification or surface grafting using benzophenone.
Scheme 20: Depolymerization mechanism of common photoresists. (a) A possible mechanism of radiation decomposit...
Scheme 21: Proposed mechanisms of photooxidative depolymerization of polystyrene. (a) Scheme 21a was reprinted with perm...
Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review
- Nosheen Beig,
- Varsha Goyal and
- Raj K. Bansal
Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102
Graphical Abstract
Scheme 1: In situ generation of imidazolylidene carbene.
Scheme 2: Hg(II) complex of NHC.
Scheme 3: Isolable and bottlable carbene reported by Arduengo [3].
Scheme 4: First air-stable carbene synthesized by Arduengo in 1992 [5].
Figure 1: General structure of an NHC.
Figure 2: Stabilization of an NHC by donation of the lone pair electrons into the vacant p-orbital (LUMO) at ...
Figure 3: Abnormal NHC reported by Bertrand [8,9].
Figure 4: Cu(d) orbital to σ*C-N(NHC) interactions in NHC–CuX complexes computed at the B3LYP/def2-SVP level ...
Figure 5: Molecular orbital contributions to the NHC–metal bond.
Scheme 5: Synthesis of NHC–Cu(I) complexes by deprotonation of NHC precursors with a base.
Scheme 6: Synthesis of [NHC–CuX] complexes.
Scheme 7: Synthesis of [(ICy)CuX] and [(It-Bu)CuX] complexes.
Scheme 8: Synthesis of iodido-bridged copper–NHC complexes by deprotonation of benzimidazolium salts reported...
Scheme 9: Synthesis of copper complexes by deprotonation of triazolium salts.
Scheme 10: Synthesis of thiazolylidene–Cu(I) complex by deprotonation with KOt-Bu.
Scheme 11: Preparation of NHC–Cu(I) complexes.
Scheme 12: Synthesis of methylmalonic acid-derived anionic [(26a,b)CuCl]Li(THF)2 and zwitterionic (28) heterol...
Scheme 13: Synthesis of diaminocarbene and diamidocarbene (DAC)–Cu(I) complexes.
Scheme 14: Synthesis of the cationic (NHC)2Cu(I) complex 39 from benzimidazolium salts 38 with tetrakis(aceton...
Scheme 15: Synthesis of NHC and ADC (acyclic diamino carbenes) Cu(I) hexamethyldisilazide complexes reported b...
Scheme 16: Synthesis of NHC–copper(I) complexes using an acetylacetonate-functionalized imidazolium zwitterion...
Scheme 17: Synthesis of NHC–Cu(I) complexes through deprotonation of azolium salts with Cu2O.
Scheme 18: Synthesis of NHC–CuBr complex through deprotonation with Cu2O reported by Kolychev [31].
Scheme 19: Synthesis of chiral NHC–CuBr complexes from phenoxyimine-imidazolium salts reported by Douthwaite a...
Scheme 20: Preparation of linear neutral NHC–CuCl complexes through the use of Cu2O. For abbreviations, please...
Scheme 21: Synthesis of abnormal-NHC–copper(I) complexes by Bertrand, Cazin and co-workers [35].
Scheme 22: Microwave-assisted synthesis of thiazolylidene/benzothiazolylidene–CuBr complexes by Bansal and co-...
Scheme 23: Synthesis of NHC–CuX complexes through transmetallation.
Scheme 24: Preparation of six- or seven-membered NHC–Cu(I) complexes through transmetalation from Ag(I) comple...
Scheme 25: Synthesis of 1,2,3-triazolylidene–CuCl complexes through transmetallation of Ag(I) complexes genera...
Scheme 26: Synthesis of NHC–copper complexes having both Cu(I) and Cu(II) units through transmetalation report...
Scheme 27: Synthesis of new [(IPr(CH2)3Si(OiPr)3)CuX] complexes and anchoring on MCM-41.
Scheme 28: Synthesis of bis(trimethylsilyl)phosphide–Cu(I)–NHC complexes through ligand displacement.
Scheme 29: Synthesis of silyl- and stannyl [(NHC)Cu−ER3] complexes.
Scheme 30: Synthesis of amido-, phenolato-, thiophenolato–Cu(NHC) complexes.
Scheme 31: Synthesis of first isolable NHC–Cu–difluoromethyl complexes reported by Sanford et al. [44].
Scheme 32: Synthesis of NHC–Cu(I)–bifluoride complexes reported by Riant, Leyssens and co-workers [45].
Scheme 33: Conjugate addition of Et2Zn to enones catalyzed by an NHC–Cu(I) complex reported by Woodward in 200...
Scheme 34: Hydrosilylation of a carbonyl group.
Scheme 35: NHC–Cu(I)-catalyzed hydrosilylation of ketones reported by Nolan et al. [48,49].
Scheme 36: Application of chiral NHC–CuCl complex 104 for the enantioselective hydrosilylation of ketones.
Scheme 37: Hydrosilylation reactions catalyzed by NHC–Cu(Ot-Bu) complexes.
Scheme 38: NHC–CuCl catalyzed carbonylative silylation of alkyl halides.
Scheme 39: Nucleophilic conjugate addition to an activated C=C bond.
Figure 6: Molecular electrostatic potential maps (MESP) of two NHC–CuX complexes computed at the B3LYP/def2-S...
Scheme 40: Conjugate addition of Grignard reagents to 3-alkyl-substituted cyclohexenones catalyzed by a chiral...
Scheme 41: NHC–copper complex-catalyzed conjugate addition of Grignard reagent to 3-substituted hexenone repor...
Scheme 42: Conjugate addition or organoaluminum reagents to β-substituted cyclic enones.
Scheme 43: Conjugate addition of boronates to acyclic α,β-unsaturated carboxylic esters, ketones, and thioeste...
Scheme 44: NHC–Cu(I)-catalyzed hydroboration of an allene reported by Hoveyda [63].
Scheme 45: Conjugate addition of Et2Zn to cyclohexenone catalyzed by NHC–Cu(I) complex derived from benzimidaz...
Scheme 46: Asymmetric conjugate addition of diethylzinc to 3-nonen-2-one catalyzed by NHC–Cu complexes derived...
Scheme 47: General scheme of a [3 + 2] cycloaddition reaction.
Scheme 48: [3 + 2] Cycloaddition of azides with alkynes catalyzed by NHC–Cu(I) complexes reported by Diez-Gonz...
Scheme 49: Application of NHC–CuCl/N-donor combination to catalyze the [3 + 2] cycloaddition of benzyl azide w...
Scheme 50: [3 + 2] Cycloaddition of azides with acetylenes catalyzed by bis(NHC)–Cu complex 131 and mixed NHC–...
Figure 7: NHC–CuCl complex 133 as catalyst for the [3 + 2] cycloaddition of alkynes with azides at room tempe...
Scheme 51: [3 + 2] Cycloaddition of a bulky azide with an alkynylpyridine using [(NHC)Cu(μ-I)2Cu(NHC)] copper ...
Scheme 52: [3 + 2] Cycloaddition of benzyl azide with phenylacetylene under homogeneous and heterogeneous cata...
Scheme 53: [3 + 2] Cycloaddition of benzyl azide with acetylenes catalyzed by bisthiazolylidene dicopper(I) co...
Figure 8: Copper (I)–NHC linear coordination polymer 137 and its conversion into tetranuclear (138) and dinuc...
Scheme 54: An A3 reaction.
Scheme 55: Synthesis of SiO2-immobilized NHC–Cu(I) catalyst 141 and its application in the A3-coupling reactio...
Scheme 56: Preparation of dual-purpose Ru@SiO2–[(NHC)CuCl] catalyst system 142 developed by Bordet, Leitner an...
Scheme 57: Application of the catalyst system Ru@SiO2–[Cu(NHC)] 142 to the one-pot tandem A3 reaction and hydr...
Scheme 58: A3 reaction of phenylacetylene with secondary amines and aldehydes catalyzed by benzothiazolylidene...
Figure 9: Kohn–Sham HOMOs of phenylacetylene and NHC–Cu(I)–phenylacetylene complex computed at the B3LYP/def2...
Figure 10: Energies of the FMOs of phenylacetylene, iminium ion, and NHC–Cu(I)–phenylacetylene complex compute...
Scheme 59: NHC–Cu(I) catalyzed diboration of ketones 147 by reacting with bis(pinacolato)diboron (148) reporte...
Scheme 60: Protoboration of terminal allenes catalyzed by NHC–Cu(I) complexes reported by Hoveyda and co-worke...
Scheme 61: NHC–CuCl-catalyzed borylation of α-alkoxyallenes to give 2-boryl-1,3-butadienes.
Scheme 62: Regioselective hydroborylation of propargylic alcohols and ethers catalyzed by NHC–CuCl complexes 1...
Scheme 63: NHC–CuOt-Bu-catalyzed semihydrogenation and hydroborylation of alkynes.
Scheme 64: Enantioselective NHC–Cu(I)-catalyzed hydroborations of 1,1-disubstituted aryl olefins reported by H...
Scheme 65: Enantioselective NHC–Cu(I)-catalyzed hydroboration of exocyclic 1,1-disubstituted alkenes reported ...
Scheme 66: Markovnikov-selective NHC–CuOH-catalyzed hydroboration of alkenes and alkynes reported by Jones et ...
Scheme 67: Dehydrogenative borylation and silylation of styrenes catalyzed by NHC–CuOt-Bu complexes developed ...
Scheme 68: N–H/C(sp2)–H carboxylation catalyzed by NHC–CuOH complexes.
Scheme 69: C–H Carboxylation of benzoxazole and benzothiazole derivatives with CO2 using a 1,2,3-triazol-5-yli...
Scheme 70: Use of Cu(I) complex derived from diethylene glycol-functionalized imidazo[1,5,a] pyridin-3-ylidene...
Scheme 71: Allylation and alkenylation of polyfluoroarenes and heteroarenes catalyzed by NHC–Cu(I) complexes r...
Scheme 72: Enantioselective C(sp2)–H allylation of (benz)oxazoles and benzothiazoles with γ,γ-disubstituted pr...
Scheme 73: C(sp2)–H arylation of arenes catalyzed by dual NHC–Cu/NHC–Pd catalytic system.
Scheme 74: C(sp2)–H Amidation of (hetero)arenes with N-chlorocarbamates/N-chloro-N-sodiocarbamates catalyzed b...
Scheme 75: NHC–CuI catalyzed thiolation of benzothiazoles and benzoxazoles.
Visible-light-induced nickel-catalyzed α-hydroxytrifluoroethylation of alkyl carboxylic acids: Access to trifluoromethyl alkyl acyloins
- Feng Chen,
- Xiu-Hua Xu,
- Zeng-Hao Chen,
- Yue Chen and
- Feng-Ling Qing
Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98
- Feng Chen Xiu-Hua Xu Zeng-Hao Chen Yue Chen Feng-Ling Qing Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China Shandong Dongyue Polymer Material Co., Ltd
Graphical Abstract
Figure 1: Selected natural products and pharmaceuticals bearing acyloins.
Scheme 1: Strategies for the synthesis of α-trifluoromethyl acyloins.
Scheme 2: Substrate scope. Standard conditions: a solution of alkyl carboxylic acid 1 (0.4 mmol), 2 (0.6 mmol...
Figure 2: Proposed reaction mechanism.
Organic thermally activated delayed fluorescence material with strained benzoguanidine donor
- Alexander C. Brannan,
- Elvie F. P. Beaumont,
- Nguyen Le Phuoc,
- George F. S. Whitehead,
- Mikko Linnolahti and
- Alexander S. Romanov
Beilstein J. Org. Chem. 2023, 19, 1289–1298, doi:10.3762/bjoc.19.95
- Information File 1). The photoluminescence (PL) characteristics of 4BGIPN have been studied in methylcyclohexane solution (MCH, concentration 3.2 × 10−5 M) and Zeonex polymer films (0.1% concentration by weight) at 298 K and 77 K, which is shown in Figure 5 with data collected in Table 3. Compound 4BGIPN
- providing ZEONEX® 480 Cyclo Olefin Polymer (COP) used in our studies. We are grateful to Dr. Louise Natrajan at the University of Manchester for providing access to FLS-1000 fluorometer. Funding This work was supported by the Royal Society and the Academy of Finland. A.S.R. acknowledges support from the
Graphical Abstract
Figure 1: The molecular structures of the title compound 4BGIPN and the benchmark TADF emitter 4CzIPN.
Figure 2: Crystal structure for compound 4BGIPN in monoclinic form ((a) top view and (b) side view) where bla...
Figure 3: Full range cyclic voltammogram for 4BGIPN. Recorded using a glassy carbon electrode in THF solution...
Figure 4: UV–vis absorption spectra for compound 4BGIPN in various solvents.
Figure 5: Photoluminescence spectra for 4BGIPN at 295 and 77 K in (top left) MCH solution; (bottom left) Zeon...
Figure 6: Energy state diagram and natural transition orbitals HONTO and LUNTO for compound 4BGIPN in excited...
Aromatic C–H bond functionalization through organocatalyzed asymmetric intermolecular aza-Friedel–Crafts reaction: a recent update
- Anup Biswas
Beilstein J. Org. Chem. 2023, 19, 956–981, doi:10.3762/bjoc.19.72
- 2020, Pedrosa and co-workers devised a chiral heterogenous thiourea catalyst that was applied in an enantioefficient aza-Friedel–Crafts process. A series of heterogenous catalysts were prepared by condensation between alkaloids and polystyrene-derived isothiocyanates. These polymer-supported materials
Graphical Abstract
Scheme 1: First organocatalyzed asymmetric aza-Friedel–Crafts reaction.
Scheme 2: Aza-Friedel–Crafts reaction between indoles and cyclic ketimines.
Scheme 3: Aza-Friedel–Crafts reaction utilizing trifluoromethyldihydrobenzoazepinoindoles as electrophiles.
Scheme 4: Aza-Friedel–Crafts reaction utilizing cyclic N-sulfimines as electrophiles.
Scheme 5: Aza-Friedel–Crafts reaction involving N-unprotected imino ester as electrophile.
Scheme 6: Aza-Friedel–Crafts and lactonization cascade.
Scheme 7: One-pot oxidation and aza-Friedel–Crafts reaction.
Scheme 8: C1 and C2-symmetric phosphoric acids as catalysts.
Scheme 9: Aza-Friedel–Crafts reaction using Nps-iminophosphonates as electrophiles.
Scheme 10: Aza-Friedel–Crafts reaction between indole and α-iminophosphonate.
Scheme 11: [2.2]-Paracyclophane-derived chiral phosphoric acids as catalyst.
Scheme 12: Aza-Friedel–Crafts reaction through ring opening of sulfamidates.
Scheme 13: Isoquinoline-1,3(2H,4H)-dione scaffolds as electrophiles.
Scheme 14: Functionalization of the carbocyclic ring of substituted indoles.
Scheme 15: Aza-Friedel–Crafts reaction between unprotected imines and aza-heterocycles.
Scheme 16: Anilines and α-naphthols as potential nucleophiles.
Scheme 17: Solvent-controlled regioselective aza-Friedel–Crafts reaction.
Scheme 18: Generating central and axial chirality via aza-Friedel–Crafts reaction.
Scheme 19: Reaction between indoles and racemic 2,3-dihydroisoxazol-3-ol derivatives.
Scheme 20: Exploiting 5-aminoisoxazoles as nucleophiles.
Scheme 21: Reaction between unsubstituted indoles and 3-alkynylated 3-hydroxy-1-oxoisoindolines.
Scheme 22: Synthesis of unnatural amino acids bearing an aza-quaternary stereocenter.
Scheme 23: Atroposelective aza-Friedel–Crafts reaction.
Scheme 24: Coupling of 5-aminopyrazole and 3H-indol-3-ones.
Scheme 25: Pyrophosphoric acid-catalyzed aza-Friedel–Crafts reaction on phenols.
Scheme 26: Squaramide-assisted aza-Friedel–Crafts reaction.
Scheme 27: Thiourea-catalyzed aza-Friedel–Crafts reaction.
Scheme 28: Squaramide-catalyzed reaction between β-naphthols and benzothiazolimines.
Scheme 29: Thiourea-catalyzed reaction between β-naphthol and isatin-derived ketamine.
Scheme 30: Quinine-derived molecule as catalyst.
Scheme 31: Cinchona alkaloid as catalyst.
Scheme 32: aza-Friedel–Crafts reaction by phase transfer catalyst.
Scheme 33: Disulfonamide-catalyzed reaction.
Scheme 34: Heterogenous thiourea-catalyzed aza-Friedel–Crafts reaction.
Scheme 35: Total synthesis of (+)-gracilamine.
Scheme 36: Total synthesis of (−)-fumimycin.
Clauson–Kaas pyrrole synthesis using diverse catalysts: a transition from conventional to greener approach
- Dileep Kumar Singh and
- Rajesh Kumar
Beilstein J. Org. Chem. 2023, 19, 928–955, doi:10.3762/bjoc.19.71
- . This methodology has been applied to diverse areas of chemistry, including natural product synthesis [45][46], medicinal chemistry [47][48], polymer chemistry [49][50] and porphyrin chemistry [51][52][53]. In recent years, green chemistry has become a widely used method for organic synthesis in order
- a mechanism for this protocol as shown in Scheme 38b. Conclusion The synthesis of pyrrole derivatives has piqued the interest of many synthetic researchers as they offer promising applications in pharmaceutical, polymer, and natural product chemistry. The introduction of a pyrrole moiety into a
- pharmaceutically active molecules, polymer synthesis, total synthesis of natural products, porphyrin functionalization, and the synthesis of various pyrrole-containing heterocyclic molecules. We believe that this review will be useful and will encourage researchers to apply the modified Clauson–Kaas reaction to
Graphical Abstract
Figure 1: Various pyrrole containing molecules.
Scheme 1: Various synthestic protocols for the synthesis of pyrroles.
Figure 2: A tree-diagram showing various conventional and green protocols for Clauson-Kaas pyrrole synthesis.
Scheme 2: A general reaction of Clauson–Kaas pyrrole synthesis and proposed mechanism.
Scheme 3: AcOH-catalyzed synthesis of pyrroles 5 and 7.
Scheme 4: Synthesis of N-substituted pyrroles 9.
Scheme 5: P2O5-catalyzed synthesis of N-substituted pyrroles 11.
Scheme 6: p-Chloropyridine hydrochloride-catalyzed synthesis of pyrroles 13.
Scheme 7: TfOH-catalyzed synthesis of N-sulfonylpyrroles 15, N-sulfonylindole 16, N-sulfonylcarbazole 17.
Scheme 8: Scandium triflate-catalyzed synthesis of N-substituted pyrroles 19.
Scheme 9: MgI2 etherate-catalyzed synthesis and proposed mechanism of N-arylpyrrole derivatives 21.
Scheme 10: Nicotinamide catalyzed synthesis of pyrroles 23.
Scheme 11: ZrOCl2∙8H2O catalyzed synthesis and proposed mechanism of pyrrole derivatives 25.
Scheme 12: AcONa catalyzed synthesis of N-substituted pyrroles 27.
Scheme 13: Squaric acid-catalyzed synthesis and proposed mechanism of N-substituted pyrroles 29.
Figure 3: Reusability of catalyst γ-Fe2O3@SiO2-Sb-IL in six cycles.
Scheme 14: Magnetic nanoparticle-supported antimony catalyst used in the synthesis of N-substituted pyrroles 31...
Scheme 15: Iron(III) chloride-catalyzed synthesis of N-substituted pyrroles 33.
Scheme 16: Copper-catalyzed Clauson–Kaas synthesis and mechanism of pyrroles 35.
Scheme 17: β-CD-SO3H-catalyzed synthesis and proposed mechanism of pyrroles 37.
Figure 4: Recyclability of β-cyclodextrin-SO3H.
Scheme 18: Solvent-free and catalyst-free synthesis and plausible mechanism of N-substituted pyrroles 39.
Scheme 19: Nano-sulfated TiO2-catalyzed synthesis of N-substituted pyrroles 41.
Figure 5: Plausible mechanism for the formation of N-substituted pyrroles catalyzed by nano-sulfated TiO2 cat...
Scheme 20: Copper nitrate-catalyzed Clauson–Kaas synthesis and mechanism of N-substituted pyrroles 43.
Scheme 21: Synthesis of N-substituted pyrroles 45 by using Co catalyst Co/NGr-C@SiO2-L.
Scheme 22: Zinc-catalyzed synthesis of N-arylpyrroles 47.
Scheme 23: Silica sulfuric acid-catalyzed synthesis of pyrrole derivatives 49.
Scheme 24: Bismuth nitrate-catalyzed synthesis of pyrroles 51.
Scheme 25: L-(+)-tartaric acid-choline chloride-catalyzed Clauson–Kaas synthesis and plausible mechanism of py...
Scheme 26: Microwave-assisted synthesis of N-substituted pyrroles 55 in AcOH or water.
Scheme 27: Synthesis of pyrrole derivatives 57 using a nano-organocatalyst.
Figure 6: Nano-ferric supported glutathione organocatalyst.
Scheme 28: Microwave-assisted synthesis of N-substituted pyrroles 59 in water.
Scheme 29: Iodine-catalyzed synthesis and proposed mechanism of pyrroles 61.
Scheme 30: H3PW12O40/SiO2-catalyzed synthesis of N-substituted pyrroles 63.
Scheme 31: Fe3O4@-γ-Fe2O3-SO3H-catalyzed synthesis of pyrroles 65.
Scheme 32: Mn(NO3)2·4H2O-catalyzed synthesis and proposed mechanism of pyrroles 67.
Scheme 33: p-TsOH∙H2O-catalyzed (method 1) and MW-assisted (method 2) synthesis of N-sulfonylpyrroles 69.
Scheme 34: ([hmim][HSO4]-catalyzed Clauson–Kaas synthesis of pyrroles 71.
Scheme 35: Synthesis of N-substituted pyrroles 73 using K-10 montmorillonite catalyst.
Scheme 36: CeCl3∙7H2O-catalyzed Clauson–Kaas synthesis of pyrroles 75.
Scheme 37: Synthesis of N-substituted pyrroles 77 using Bi(NO3)3∙5H2O.
Scheme 38: Oxone-catalyzed synthesis and proposed mechanism of N-substituted pyrroles 79.
Cyclodextrins as building blocks for new materials
- Miriana Kfoury and
- Sophie Fourmentin
Beilstein J. Org. Chem. 2023, 19, 889–891, doi:10.3762/bjoc.19.66
- biocompatible. Thus, these supra-architectures have a multitude of uses in food, biomedicine, regenerative medicine, cosmetics, molecular electronics, polymer chemistry, gold recovery, gas absorption, depollution, biochemical material sciences, nanotechnology, self-healing materials, 3D printing, and so on [19
Light-responsive rotaxane-based materials: inducing motion in the solid state
- Adrian Saura-Sanmartin
Beilstein J. Org. Chem. 2023, 19, 873–880, doi:10.3762/bjoc.19.64
- ) Chemical structure of polyrotaxane 2; and (b) cartoon representation of the light-triggered degradation of rotaxane polymer 2 [52]. The key colour of the cartoon representation is analogous to that of the chemical structures. a) Chemical structures of rotaxanes (E)-3 and (Z)-3; b) stick representation of
Graphical Abstract
Figure 1: a) Chemical structure of pseudorotaxanes 1; and (b) single-crystal X-ray structure of rotaxane 1a (R...
Figure 2: (a) Chemical structure of polyrotaxane 2; and (b) cartoon representation of the light-triggered deg...
Figure 3: a) Chemical structures of rotaxanes (E)-3 and (Z)-3; b) stick representation of the solid structure...
Figure 4: Stick representations of the solid structures of: (a) U-CB[8]-MPyVB showing an interlocked ligand c...
pH-Responsive fluorescent supramolecular nanoparticles based on tetraphenylethylene-labelled chitosan and a six-fold carboxylated tribenzotriquinacene
- Nan Yang,
- Yi-Yan Zhu,
- Wei-Xiu Lin,
- Yi-Long Lu and
- Wen-Rong Xu
Beilstein J. Org. Chem. 2023, 19, 635–645, doi:10.3762/bjoc.19.45
- labelling of hydrophobic TPE fluorogens, reducing the affinity of the CS chains to the aqueous medium and resulting in the entanglement or wrapping of the TPE fluorogens by polymer chains. As a result, the RIR process was enhanced, greatly increasing the fluorescence. In addition, the fluorescence intensity
- improved water solubility of the supra-amphiphile due to the highly water-soluble behavior of TBTQ-C6 under alkaline conditions in its carboxyl anion form. As a result, the polymer chains were extended, releasing the entanglement and wrapping of the TPE fluorogens, thereby reducing the emission of the
- successfully designed and synthesized different degrees of TPE-labelled CS polymer compounds that exhibit the AIE fluorescence effect and we constructed pH-responsive fluorescent supramolecular spherical nanoparticles based on CS-TPE alone and the host–guest TBTQ-C6/CS-TPE supra-amphiphile. The critical
Graphical Abstract
Scheme 1: (a) Synthesis route to CS-TPE. (b) Structure of TBTQ-C6. (c) Construction of TBTQ-C6/CS-TPE supramo...
Figure 1: Partial 1H NMR spectra (400 MHz, CD3COOD/D2O, 25 °C) of (a) CS, (b) CS-TPE-2%, (c) CS-TPE-10%, and ...
Figure 2: (a) Optical images of CS-TPE under daylight (top) and 365 nm UV light (bottom) in the solid state; ...
Figure 3: TEM images of (a) CS-TPE-2%, (b) CS-TPE-10%, and (c) CS-TPE-20% assemblies at pH 5.3; TEM images of...
Figure 4: (a, c, e) Optical transmittance and (b, d, f) transmittance as a function of [TBTQ-C6] at 293 nm of...
Figure 5: (a, c, e) Optical transmittance and (b, d, f) CS-TPE concentration-dependent optical transmittance ...
Figure 6: TEM images of (a) TBTQ-C6/CS-TPE-10% in aqueous solution at pH 5.3, (b) after adjustment of the sol...
Figure 7: (a) Fluorescence spectra of CS-TPE with different Rf in aqueous solutions at pH 5.3 and 10.4; (b) f...
