20492-13-1Relevant articles and documents
Spiro Rhodamine-Perylene Compact Electron Donor-Acceptor Dyads: Conformation Restriction, Charge Separation, and Spin-Orbit Charge Transfer Intersystem Crossing
Elmali, Ayhan,Hu, Mengyu,Ji, Shaomin,Karatay, Ahmet,Sukhanov, Andrei A.,Voronkova, Violeta K.,Zhang, Xue,Zhao, Jianzhang
, p. 4187 - 4203 (2021)
Spiro rhodamine (Rho)-perylene (Pery) electron donor-acceptor dyads were prepared to study the spin-orbit charge transfer intersystem crossing (SOCT-ISC) in these rigid and sterically congested molecular systems. The electron-donor Rho (lactam form) moiety is attached via the N-C bond to the electron acceptor at either 1- or 3-position of the Pery moiety (Rho-Pery-1 and Rho-Pery-3). Severe torsion of the Pery moiety in Rho-Pery-1 was observed. The fluorescence of the two dyads is significantly quenched in polar solvents, and the singlet oxygen quantum yields (φδ) are strongly dependent on solvent polarity (4-36%). Femtosecond transient absorption spectra demonstrate that charge separation (CS) takes 0.51 ps in Rho-Pery-1 and 5.75 ps in Rho-Pery-3, and the charge recombination (CR)-induced ISC is slow (>3 ns). Nanosecond transient absorption spectra indicate that the formation of triplet states via SOCT-ISC takes 24-75 ns for Rho-Pery-1 and 6-15 ns for Rho-Pery-3, and the distorted π-framework of the Pery moiety results in a shorter triplet lifetime of 19.9 vs 291 μs for the planar analogue. Time-resolved electron paramagnetic resonance spectroscopy confirms the SOCT-ISC mechanism.
The effects of 1-and 3-positions substitutions on the photophysical properties of perylene and its application in thiol fluorescent probes
He, Qin,Dong, Fangdi,Xing, Longjiang,He, Huahong,Chen, Xiaoping,Wang, Huaqian,Ji, Shaomin,Huo, Yanping
, (2021/12/02)
A series of perylene derivatives bearing electron-donating group (amino) and electron-withdrawing group (nitro, maleimide) at the 1- and 3-position have been synthesized. Interestingly, 3-monosubstituted perylenes shown different photophysical properties compared with 1-monosubstituted perylenes. 3-nitroperylene (3-NO) attained 80.62% photoluminescence quantum yield (ΦPL) in toluene which is higher than 3-aminoperylene (3-NH, ΦPL = 71.70%) and 1-aminoperylene (1-NH, ΦPL = 48.04%), but for 1-nitroperylene (1-NO), no fluorescence in any solvent were observed. The calculated ground-state geometries of 3-monosubstituted perylenes actually correspond to nearly planar structures, but the molecules substituted at the 1-position all have a twisted structure. Among them, 3-NO had a great π-conjugated system, resulting in the allowed ππ? fluorescence. In contrast, the twisting structure of 1-NO enhanced nonradiative decay pathways, coupled with the electron-withdrawing effect of the nitro group, which can explain the non-luminescence of 1-NO. Furthermore, the moleculars with maleimide group were used as “off-on” fluorescent probes and successfully used for imaging biothiols in living H1299 lung cancer cells. The fluorescence of probe 2 (substitutes at 3-position of perylene) afforded a 188-fold intensity increase after reaction with thiol which is much higher than (65-fold) probe 1 (substitutes at 1-position) because of the better π-conjugated structure. We envision that the investigation on the effects of substitute at 1-and 3-positions of perylene may be helpful for a rational design and application of highly fluorescent molecule base on perylene.
Perylene-based small molecular fluorescent probe and preparation method and application thereof
-
Paragraph 0064; 0065; 0066; 0067; 0068; 0069-0073, (2018/03/24)
The invention belongs to the technical field of sulfhydryl biological small molecule detection, in particular to a perylene-based small molecular fluorescent probe and a preparation method and application thereof. The preparation method comprises the following steps: first performing a nitration reaction on 1-position carbon or 3-position carbon of perylene so as to connect a nitro group, then reducing the nitro group into an amino group, then replacing the amino group with maleic anhydride so as to obtain two small molecular fluorescent probes adopting novel structures, provided by the invention, wherein the two small molecular fluorescent probes adopts the chemical structural formulae shown as a formula (I) or a formula (II). When the small molecular fluorescent probe is combined with a sulfhydryl biological small molecule in a biological cell, green light is emitted, which is significantly different from background blue light of the biological cell; the small molecular fluorescent probe has the advantages of high sensitivity, good selectivity and low biological toxicity; in addition, the preparation process is simple and optimized, and the detection cost of the sulfhydryl biological small molecule is greatly reduced.
Highly fluorescent complexes with 3-isocyanoperylene and N-(2,5-di-tert-butylphenyl)-9-isocyano-perylene-3,4-dicarboximide
Lentijo,Exposito,Aullon,Miguel,Espinet
, p. 10885 - 10897 (2014/07/08)
The perylene derivatives 3-isocyanoperylene (Per-NC) (4a) and N-(2,5-di-tert-butylphenyl)-9-isocyano-perylene-3,4-dicarboximide (PMI-NC) (4b) were prepared and used to synthesize gold complexes [AuX(CNR)] (X = C 6F5 (5a,b), C6F4-OnBu-p (6b)). The reaction of 5b and 6b with HNEt2 led to the carbene complexes [AuX{C(NEt2)(NHR)}] (7b, 8b), respectively. The molecular structure of complexes 7b and 8b have been determined by X-ray diffraction analysis showing intermolecular π-stacking of the perylene groups and C 6F5 rings and no Au...Au interactions. The derivative compounds [M(CO)5(CNR)] (M = Cr (9a,b), Mo (10a,b) or W (11a,b)) and trans-[Pd(CNR)2(C6F3Cl2) 2] (12a,b) were also prepared. All complexes exhibit fluorescence associated with the perylene fragment with emission quantum yields, in solution at room temperature, in the range 0.05-0.93 and emission lifetimes ～ 4 ns. DFT calculations were performed of the absorption spectra of the ligands Per-NC and PMI-NC and representative complexes [Au(C6F5)(CNR)], [Cr(CO)5(CNR)], showing a perylene-dominated intraligand π-π* emissive state, from the HOMO and LUMO orbitals of the perylene chromophore, but with significantly different absorption maxima by the influence of the metal fragment, particularly significant in the Per-NC derivatives.
Solution-processable organic fluorescent dyes for multicolor emission in organic light emitting diodes
Pu, Yong-Jin,Higashidate, Makoto,Nakayama, Ken-Ichi,Kido, Junji
supporting information; experimental part, p. 4183 - 4188 (2010/03/03)
Four novel fluorescent dyes, bis(difluorenyl)amino-substituted carbazole 1, pyrene 2, perylene 3, and benzothiadiazole 4, were synthesized by C-N cross-coupling with a palladium catalyst. These dyes are soluble in common organic solvents, and their uniform films were formed by spin-coating from their solutions. Their glass transition temperatures were sufficiently high (120-181°C) to form amorphous films for organic light emitting diodes. These solution processable dyes exhibited strong photoluminescence (PL) in the film form (1: sky blue, 2: blue-green, 3: yellow, and 4: deep red). Optical and electrochemical properties of the compounds were investigated with photoelectron spectroscopy and cyclic voltammetry. The energy levels obtained from both measurements were in good agreement, and those levels were related to the electronic properties of the central core; the electron-donating carbazole compound showed the lowest ionization potential and the electron-withdrawing benzothiadiazole compound showed the largest electron affinity. Simple double layer devices were prepared with these fluorescent dyes as emitting layer and bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminium(iii) (BAlq) as a common hole blocking layer for each color. Electroluminescence colors were the same as those of the PL spectra in each compound. These multicolor electroluminescences show that these conjugated oligomers can be candidates for solution processable light emitting materials for OLEDs as well as conjugated polymers or dendrimers.
Light-Induced Charge Separation by Formation of Insoluble Precipitates
Grabner, Erich Walter,Hessberger, Harald
, p. 226 - 230 (2007/10/02)
Preliminary experiments are reported on light-induced charge separation by quenching electronically excited species with formation of insoluble precipitates.Irradiation of acceptor-donor mixtures of 3-dimethylaminoperylene metaphosphate/tetramethyl-p-phenylenediamine (TMPD) and of Ag+/perylene, respectively, in methylene chloride and with tetrabutylammonium perchlorate as supporing electrolyte formed precipitates of TMPD+ClO4- and Ag, respectively.The precipitates were separated from the solution by a platinum filter in a flow cell, which served as a simple battery for conversion of stored chemical energy into electrical energy.The quantum yield was about 1E-6 and the battery voltage about 60 mV.
