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1.
Org Biomol Chem ; 21(23): 4881-4892, 2023 Jun 14.
Artículo en Inglés | MEDLINE | ID: mdl-37259536

RESUMEN

An aminomethylation reaction of fulleropyrrolidines bearing ketone moieties in the presence of N-unsubstituted fulleropyrrolidines and paraformaldehyde with the aid of p-toluenesulfonic acid afforded a series of scarce pendant fullerene dimers. A simple change of reaction substrates from ketone to ketone-containing fulleropyrrolidines successfully realized the synthesis of a variety of novel pendant fullerene dimers, including those from methyl ketone-containing fulleropyrrolidines, which were considered to produce the known bridged fullerene dimers. It should be noted that pendant fullerene dimers are usually difficult to prepare by other methods and may have promising applications in perovskite solar cells. Density functional theory (DFT) has been employed to elucidate the regioselectivity of methyl ketone-containing fulleropyrrolidines to yield exclusively pendant fullerene dimers by investigating the Gibbs free energy profile of the reaction starting from methyl ketone-containing fulleropyrrolidines and iminium intermediates.

2.
Inorg Chem ; 60(7): 4841-4851, 2021 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-33711236

RESUMEN

Luminescent copper(I) halide complexes with bi- and tridentate rigid ligands have gained wide research interests. In this paper, six tetracoordinate dinuclear copper(I) halide complexes, Cu2X2(ppda)2 [ppda = 2-[2-(dimethylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline, X = I (1), Br (2), Cl (3)] and Cu2X2(pfda)2 [pfda = 2-[2-(dimethylamino)-4-(trifluoromethyl)phenyl(phenyl)phosphino]-N,N-dimethyl-5-trifluoromethylaniline, X = I (4), Br (5), Cl (6)], were successfully prepared and systematically characterized on their structures and photophysical properties. Complexes 1-5 have a centrosymmetric form with a planar Cu2X2 unit, and complex 6 has a mirror symmetry form with a butterfly-shaped Cu2X2. Solid complexes 1, 4, and 5 emit delayed fluorescence at room temperature, intense blue to greenish yellow (λmax = 443-570 nm) light, and their peak wavelengths are located at 443-570 nm with microsecond lifetimes (τ = 0.4-19.2 µs, ΦPL = 0.05-0.48). Complexes 2, 3, and 6 show prompt fluorescence, very weak yellowish green to yellow (λmax = 534-595 nm) emission with peak wavelengths at 534-595 nm, and lifetimes in nanoseconds (τ = 4.4-9.3 ns, ΦPL < 0.0001). (Metal + halide) to ligand and intraligand charge transitions are the main origin of the emission of the complexes. Solution-processed, complex-4-based nondoped and doped devices emit yellow green light with CIE coordinated at (0.41, 0.51), a maximum EQE up to 0.17%, and luminance reaching 75.52 cd/m2.

3.
Org Biomol Chem ; 19(46): 10139-10155, 2021 12 01.
Artículo en Inglés | MEDLINE | ID: mdl-34768279

RESUMEN

The simple one-step reaction of [60]fullerene with α-monosubstituted acetaldehydes and primary amines in the presence of Mn(OAc)3·2H2O under air conditions afforded a series of novel N-substituted fulleropyrrolines with trisubstituted CC bonds in moderate to good yields. The addition of Mn(OAc)3·2H2O played a crucial role in the successful synthesis of N-aryl fulleropyrrolines with trisubstituted CC bonds, which would be extremely difficult to prepare by known methods as a result of the decreased nucleophilicity of arylamines due to the p-π conjugation effect. Intriguingly, arylamines displayed abnormally higher reactivity as compared with non-arylamines in the current reaction system by the observation of obviously decreased equivalent of Mn(OAc)3·2H2O, higher product yields, and lower reaction temperature probably due to the radical reaction mechanism initiated by Mn(OAc)3·2H2O. On the basis of experimental observations, a plausible formation pathway for N-substituted fulleropyrrolines with trisubstituted CC bonds was proposed to elucidate the above-mentioned reaction process.

4.
Org Biomol Chem ; 18(35): 6866-6880, 2020 09 21.
Artículo en Inglés | MEDLINE | ID: mdl-32844859

RESUMEN

A series of scarce amino-substituted cyclopentafullerenes instead of the expected N-alkyl-2,5-disubstituted fulleropyrrolidines were synthesized in moderate to excellent yields via the simple one-step reaction of [60]fullerene with cheap and easily available ß-substituted propionaldehydes and secondary amines in the absence/presence of magnesium perchlorate. The in situ generation of allylic amines from ß-substituted propionaldehydes and secondary amines played a crucial role in the successful preparation of amino-substituted cyclopentafullerenes without additional carbons. With the addition of magnesium perchlorate, secondary amines containing ethyl group(s) could produce novel amino-substituted cyclopentafullerenes with two additional carbons. All the obtained cyclopentafullerenes displayed high stereoselectivity with cis isomers as the exclusive or major products. Plausible reaction mechanisms are proposed to elucidate the above-mentioned reaction process.

5.
Org Biomol Chem ; 18(5): 964-974, 2020 02 07.
Artículo en Inglés | MEDLINE | ID: mdl-31930265

RESUMEN

A facile one-step reaction of [60]fullerene with cinnamaldehydes and amines promoted by magnesium perchlorate/ferric perchlorate under air conditions afforded a series of rare amino-substituted cyclopentafullerenes in moderate to good yields. Stereoselectivity was readily achieved. Secondary amines exclusively produced N,N-disubstituted cyclopentafullerenes as cis isomers, while arylamines gave N-monosubstituted cyclopentafullerenes with a preference of cis isomers as major products. N-Monosubstituted cyclopentafullerenes could be further converted into other scarce cyclopentafullerenes in the presence of acid chloride or paraformaldehyde. A possible reaction pathway was proposed to elucidate the formation of amino-substituted cyclopentafullerenes.

6.
J Org Chem ; 84(5): 2922-2932, 2019 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-30729784

RESUMEN

A series of scarce N-alkyl-2,5-unsubstituted/monosubstituted fulleropyrrolidines were synthesized in moderate to excellent yields by the simple one-step thermal reaction of [60]fullerene with primary/secondary amines in the presence of paraformaldehyde without the addition of valuable metal salts. Intriguingly, the reaction with primary amines unexpectedly afforded N-alkyl-2,5-unsubstituted fulleropyrrolidines instead of the anticipated 2,5-monosubstituted fulleropyrrolidines. A plausible reaction pathway is proposed to elucidate the above-mentioned reaction process based on the experimental results.

7.
J Org Chem ; 83(1): 85-95, 2018 01 05.
Artículo en Inglés | MEDLINE | ID: mdl-29231732

RESUMEN

A series of scarce tetrahydropyridinofullerenes were synthesized by the metal-free-mediated reaction of [60]fullerene with cheap and easily available α-methyl-substituted arylmethanamines and aldehydes in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-dimethylaminopyridine (DMAP) in moderate to good yields comparable to the previously reported data for most monoadducts. The in situ generation of azadienes played a crucial role in the successful synthesis of tetrahydropyridinofullerenes. A plausible reaction mechanism was proposed to elucidate the reaction process.

8.
Org Biomol Chem ; 16(41): 7648-7656, 2018 11 07.
Artículo en Inglés | MEDLINE | ID: mdl-30283968

RESUMEN

A series of scarce fulleropyrrolidin-2-ols were synthesized by the facile one-step reaction of [60] fullerene with inexpensive and readily accessible amines and 2,2-disubstituted acetaldehydes without the addition of valuable metal salts in moderate yields, comparable to those for most monoadducts reported previously. This strategy exhibits a broad substrate scope and excellent functional group tolerance. A plausible reaction pathway for the formation of fulleropyrrolidin-2-ols is proposed to elucidate the above reaction process.

9.
Org Biomol Chem ; 16(16): 2975-2985, 2018 04 25.
Artículo en Inglés | MEDLINE | ID: mdl-29623972

RESUMEN

The reaction of [60]fullerene with aromatic aldehydes and triethylamine/diethylamine in the absence or presence of manganese(iii) acetate under air conditions afforded a series of N-ethyl-2-arylvinyl-5-methyl fulleropyrrolidines in moderate to good yields, which would be difficult to synthesize by reported protocols. The in situ generation of arylvinyl aldehydes by the aldol reaction of aromatic aldehydes with acetaldehyde from an unusual C-N bond cleavage of triethylamine/diethylamine played a crucial role in the successful preparation of the corresponding fulleropyrrolidines. Depending on the reaction conditions, both cis and trans isomers of fulleropyrrolidines could be selectively synthesized. Cis isomers as major products could be obtained by reacting with triethylamine at 160 °C without the addition of manganese(iii) acetate, while trans isomers as major products, with rare exceptions, could be observed via the reaction with diethylamine at 120 °C under the assistance of manganese(iii) acetate. Moreover, the in situ generated arylvinyl aldehydes displayed higher reactivity towards diethylamine as compared with aryl aldehydes, leading to the formation of arylvinyl-substituted fulleropyrrolidines. A plausible formation mechanism for fulleropyrrolidines was provided based on the experimental observations.

10.
J Org Chem ; 82(16): 8617-8627, 2017 08 18.
Artículo en Inglés | MEDLINE | ID: mdl-28756668

RESUMEN

The metal-free-mediated thermal reaction of [60]fullerene with aromatic aldehydes and inactive primary amines bearing electron-donating groups at the α-position afforded a series of 2-aryl-5-alkyl-fulleropyrrolidines, including the scarce 2-aryl-5-benzyl-fulleropyrrolidines as a mixture of cis and trans isomers. With rare exceptions, the mixture of cis and trans isomers could be easily isolated by column chromatography, with a preference of cis isomers as major products. A plausible mechanism for the formation of fulleropyrrolidines is also proposed.

11.
J Org Chem ; 82(18): 9751-9764, 2017 09 15.
Artículo en Inglés | MEDLINE | ID: mdl-28849930

RESUMEN

A series of scarce fulleropyrrolines were synthesized via DMAP-mediated one-step reaction of [60]fullerene with commercially inexpensive aromatic aldehydes and arylmethanamines in the absence or presence of manganese(III) acetate. In the case of aminodiphenylmethane, novel 2,5,5-trisubstituted fulleropyrrolines could be easily obtained without the addition of manganese(III) acetate. As for arylmethanamines without α-substitutions, the addition of manganese(III) acetate was required to suppress the formation of fulleropyrrolidines, in order to generate the desired 2,5-disubstituted fulleropyrrolines. Two tautomers were produced as expected when different aryl groups (Ar1 ≠ Ar2) from aromatic aldehydes and arylmethanamines were employed in the synthesis. A plausible reaction mechanism for the formation of fulleropyrrolines is proposed.

12.
J Org Chem ; 81(19): 9296-9307, 2016 10 07.
Artículo en Inglés | MEDLINE | ID: mdl-27654104

RESUMEN

The facile one-step reaction of [60]fullerene with aldehydes and primary amines in the presence of cheap and easily available Cu(OAc)2·H2O afforded a series of new types of fulleropyrrolines with trisubstituted C═C bonds in good to excellent yields, which would be difficult to prepare by known methods. The formed fulleropyrroline under the assistance of Pd(OAc)2 and CuCl2·2H2O could be further converted to 1-fulleropyrrolidine by the chlorohydroxylation reaction of C═C bond. Subsequent elimination reaction of 1-fulleropyrrolidine with the aid of TsOH·H2O generated the scarce 1-fulleropyrroline derivative.

13.
J Org Chem ; 81(5): 1769-77, 2016 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-26841702

RESUMEN

A series of scarce N-unsubstituted 2,5-diaryl fulleropyrrolidines as cis isomers could be prepared via the facile one-step reaction of [60]fullerene with N-unsubstituted arylmethanamines promoted by cheap and easily available ferric perchlorate. Nevertheless, the reaction of N-substituted arylmethanamines with [60]fullerene under the same conditions gave different experimental results. N-Methylbenzylamine formed N-methyl 2,5-diphenyl fulleropyrrolidine as a trans isomer, and N,N-dibenzylamine unexpectedly afforded the N-unsubstituted 2,5-diphenyl fulleropyrrolidine as a cis isomer. Intriguingly, high stereoselectivity for all 2,5-diaryl fulleropyrrolidines could be observed although both cis and trans isomers were possibly formed. N-Unsubstituted fulleropyrrolidine could be further converted to N-substituted fulleropyrrolidines under the assistance of an acid chloride or an isocyanate. A possible reaction pathway leading to 2,5-diaryl fulleropyrrolidines is also proposed.

14.
J Org Chem ; 81(17): 7662-74, 2016 09 02.
Artículo en Inglés | MEDLINE | ID: mdl-27471871

RESUMEN

Thermal reaction of [60]fullerene with various arylmethanamines in the presence of aromatic aldehydes under air conditions afforded a series of rare 2,5-diaryl fulleropyrrolidines. Intriguingly, the obtained fulleropyrrolidines exhibited different stereoselectivity. N-unsubstituted arylmethanamines exclusively produced 2,5-diaryl fulleropyrrolidines as cis isomers, while N-substituted arylmethanamines with rare exceptions always gave 2,5-diaryl fulleropyrrolidines as trans isomers. Theoretical calculations at the level of B3LYP/6-31G (d,p) were employed to elucidate the stereoselectivity of N-substituted 2,5-diaryl fulleropyrrolidines as trans isomers by investigating the transition-state structures of different cycloaddition pathways.

15.
J Org Chem ; 80(24): 11986-92, 2015 Dec 18.
Artículo en Inglés | MEDLINE | ID: mdl-26595850

RESUMEN

The rare fulleroxazolidines 2 were successfully synthesized by the facile ferric perchlorate promoted reaction of [60]fullerene with various N-sulfonyl aldimines 1. Further functionalization of fulleroxazolidines by arenes in the presence of boron trifluoride afforded 1,4-bisarylation products 4. A possible reaction mechanism for the formation of the fulleroxazolidines is proposed.

16.
J Org Chem ; 80(12): 6037-43, 2015 Jun 19.
Artículo en Inglés | MEDLINE | ID: mdl-25996442

RESUMEN

The facile one-step reaction of [60]fullerene with various diols in the presence of ferric perchlorate afforded a series of rare fullerene-fused dioxanes/dioxepanes. Nevertheless, the reaction of [60]fullerene with diethylene glycol, triethylene glycol, and tripropylene glycol promoted by ferric perchlorate unexpectedly generated fullerene-fused dioxanes instead of the anticipated fullerene-fused crown ethers. A plausible reaction mechanism is proposed to explain the formation of fullerene-fused dioxane/dioxepane products.

17.
J Org Chem ; 79(22): 11155-60, 2014 Nov 21.
Artículo en Inglés | MEDLINE | ID: mdl-25360886

RESUMEN

A lead(IV) acetate-promoted radical reaction of [60]fullerene with halocarboxylic acids has been exploited to synthesize rare ortho acid ester-type 1,3-dioxolanofullerenes, the hydroxyl group of which can be further transformed to an ester or ether group. Intriguingly, an ortho acid ester-type 1,3-dioxolanofullerene can also be converted to a 1,4-dioxanonofullerene in the presence of a base or manipulated to another ortho acid ester-type 1,3-dioxolanofullerene by reaction with a stronger halocarboxylic acid. Moreover, two possible reaction pathways leading to the observed products are also proposed.


Asunto(s)
Ácidos Carboxílicos/química , Fulerenos/química , Hidrocarburos Halogenados/química , Plomo/química , Ésteres , Espectroscopía de Resonancia Magnética
18.
J Org Chem ; 79(3): 1487-92, 2014 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-24397372

RESUMEN

The BF3·Et2O-catalyzed formal [3 + 2] reaction of aziridinofullerenes with various carbonyl compounds for the easy preparation of fullerooxazolidines has been developed. Moreover, the reaction of aziridinofullerene with ethyl formate affords the simplest fullerooxazole without substituent.


Asunto(s)
Aziridinas/química , Compuestos de Boro/química , Fulerenos/química , Oxazoles/química , Catálisis , Estructura Molecular
19.
J Org Chem ; 77(15): 6643-7, 2012 Aug 03.
Artículo en Inglés | MEDLINE | ID: mdl-22804566

RESUMEN

1,2-Fullerenols C(60)(OCOR)(OH) have been facilely synthesized via the one-step reaction of [60]fullerene with acid chlorides promoted by ferric perchlorate. A possible reaction mechanism for the product formation is proposed.


Asunto(s)
Compuestos Férricos/química , Fulerenos/química , Percloratos/química , Estructura Molecular
20.
Dalton Trans ; 49(18): 5859-5868, 2020 May 14.
Artículo en Inglés | MEDLINE | ID: mdl-32307473

RESUMEN

Highly emissive copper(i) halide nanoclusters showing thermally activated delayed fluorescence (TADF) have been paid much attention, but rarely reported so far. Herein, a hexanuclear copper(i) iodide cluster containing a tridentate N∧P∧N ligand, [Cu6I6(ppda)2] {ppda = 2-[2-(dimethylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline}, was synthesized. All six copper atoms are four-coordinate, including four CuPNI2 and two CuI4 units. This complex exhibits intense white emission in the powder state at room temperature and shows a peak at a wavelength of 535 nm (ΦPL = 0.36) with a microsecond lifetime (τ = 4.4 µs). Emission colors can be largely tuned from blue to white to yellow, from the crystal to powder to film state at 297 K. The emission of [Cu6I6(ppda)2] originates from a combination of MLCT and XLCT transitions. This complex showed good thermal stability. A solution-processed, nondoped device of complex [Cu6I6(ppda)2] exhibits stable yellow emission with the CIE coordinates (x, y) of (0.43, 0.51). [Cu6I6(ppda)2] also shows reasonable photocatalytic H2 evolution activity under visible-light irradiation.

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