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1.
Molecules ; 27(9)2022 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-35566117

RESUMO

Herein, we report the synthesis of sulfur-substituted boron(III) subphthalocyanines (SubPcs) with cationic axial ligands. Subphthalocyanines were synthesized by a condensation reaction using the corresponding phthalonitriles and boron trichloride as a template. An aminoalkyl group was introduced on the central boron atom; this process was followed by N-methylation to introduce a cationic axial ligand. The peripheral sulfur groups shifted the Q band of SubPcs to a longer wavelength. The cationic axial ligands increased the polarity and enhanced the hydrophilicity of SubPcs. The effect of axial ligands on absorption and fluorescence properties is generally small. However, a further red shift was observed by introducing cationic axial ligands into the sulfur-substituted SubPcs. This change is similar to that in sulfur-substituted silicon(IV) phthalocyanines. The unique effect of the cationic axial ligand was extensively investigated by theoretical calculations and electrochemistry. In particular, the precise oxidation potential was determined using ionization potential measurements. Thus, the results of the present study provide a novel strategy for developing functional dyes and pigments based on SubPcs.


Assuntos
Boro , Indóis , Boro/química , Cátions , Indóis/química , Ligantes , Enxofre
2.
Chemistry ; 28(2): e202103223, 2022 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-34734432

RESUMO

The high penetration of near-infrared (NIR) light makes it effective for use in selective reactions under light-shielded conditions, such as in sealed reactors and deep tissues. Herein, we report the development of phthalocyanine catalysts directly activated by NIR light to transform small organic molecules. The desired photocatalytic properties were achieved in the phthalocyanines by introducing the appropriate peripheral substituents and central metal. These phthalocyanine photocatalysts promote cross-dehydrogenative-coupling (CDC) under irradiation with 810 nm NIR light. The choice of solvent is important, and a mixture of a reaction-accelerating (pyridine) and -decelerating (methanol) solvents was particularly effective. Moreover, we demonstrate photoreactions under visible-light-shielded conditions through the transmission of NIR light. A combined experimental and computational mechanistic analysis revealed that this NIR reaction does not involve a photoredox-type mechanism with electron transfer, but instead a singlet-oxygen-mediated mechanism with energy transfer.


Assuntos
Indóis , Isoindóis , Raios Infravermelhos , Oxigênio Singlete
3.
Chem Commun (Camb) ; 57(99): 13594-13597, 2021 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-34850783

RESUMO

Phthalocyanine ruthenium complexes were identified as red-light activatable catalysts for trifluoromethylation reactions. The red-light mediated chlorotrifluoromethylation of alkenes could proceed without any sacrificial reducing reagents. This reaction exhibited good compatibility with a blue-light-absorbing substrate, while under irradiation with blue light, i.e., under traditional photoreaction conditions, this substrate decomposed completely.

4.
Small ; 17(47): e2104458, 2021 11.
Artigo em Inglês | MEDLINE | ID: mdl-34643043

RESUMO

Efficient excitation of a triplet (T1 ) state of a molecule has far-reaching effects on photochemical reaction and energy conversion systems. Because the optical transition from a ground singlet (S0 ) to a T1 state is spin-forbidden, a T1 state is generated via intersystem crossing (ISC) from an excited singlet (S1 ) state. Although the excitation efficiency of a T1 state can be increased by enhancing ISC utilizing a heavy atom effect, energy loss during S1 →T1 relaxation is inevitable. Here, a general approach to directly excite a T1 state from a ground S0 state via magnetic dipole transition, which is boosted by enhanced magnetic field induced by a dielectric metasurface, is proposed. As a dielectric metasurface, a hexagonal array of silicon (Si) nanodisks is employed; the nanodisk array induces a strongly enhanced magnetic field on the surface due to the toroidal dipole (TD) resonance. A proof-of-concept experiment is performed using ruthenium (Ru) complexes placed on a metasurface and demonstrates that the phosphorescence is 35-fold enhanced on a metasurface when the TD resonance is tuned to the wavelength of the direct S0 →T1 transition. These results indicate that photon energy necessary to excite the T1 state can be reduced by more than 400 meV compared to the process involving the ISC. By combining optical measurements with numerical simulations, the mechanism of the phosphorescence enhancement is quantitatively discussed.


Assuntos
Campos Magnéticos , Vibração
5.
Chem Pharm Bull (Tokyo) ; 69(6): 526-528, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34078798

RESUMO

The optical property of fluorescent unit-conjugated aliphatic oxaboroles has been investigated. The oxaboroles provide good fluorescence quantum yields and selective recognition toward D-ribose and D-ribose containing molecules. The molecular recognition induced significant fluorescence quenching. The property of the boroles showed the possibility of the boron-based nicotinamide adenine dinucleotide (NAD) sensor probe.


Assuntos
Compostos de Boro/química , Corantes Fluorescentes/química , NAD/química , Açúcares/análise , Compostos de Boro/síntese química , Corantes Fluorescentes/síntese química , Estrutura Molecular , Fenômenos Ópticos
6.
Dalton Trans ; 50(18): 6245-6255, 2021 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-33876177

RESUMO

Reaction of (2,3,9,10,16,17,23,24-octabutylphthalocyaninato)lanthanide(iii) acetylacetonates (BuPcLn(acac), 1a-c, Ln = Lu (a), Eu (b), La (c)) with a tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazine ligand (tBuPhDzPzH2, 2) produced sandwich compounds (tBuPhDzPz)Ln(BuPc) (3a-c), which represent the first heteroleptic double-deckers incorporating both Pc and DzPz decks. A combination of high-resolution mass spectrometry, UV-Vis/NIR, MCD, and 1H NMR spectroscopy, and square-wave voltammetry provided unambiguous characterization of target complexes 3 indicating that their spectral and electrochemical properties are generally intermediate with respect to their homoleptic relatives. Based on the data of solution-state 1H-1H NMR (COSY, NOESY) correlation spectroscopy supported by DFT calculations, a dimerization tendency of compounds 3 proportional to the Ln(iii) ion size was found. The spectroelectrochemical study of 3 and the corresponding homoleptic double-deckers revealed a pronounced tendency to aggregation of the one-electron oxidized forms of DzPz-containing double-decker complexes compared to homoleptic Pc2Ln compounds.

7.
J Org Chem ; 86(4): 3625-3636, 2021 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-33555890

RESUMO

To improve the efficiency of the photocatalytic decarbonylation of cyclopropenones, the effects of substituents on cyclopropenone were explored. A benzothiophene-substituted aminocyclopropenone exhibited significantly improved decarbonylation efficiency to produce the corresponding ynamine, which worked as a potent dehydration condensation agent. The benzothiophene derivative was applicable to the photocatalytic reaction in the presence of potential excited-state quenchers such as oxygen and anilines. The high catalyst sensitivity would be attributed to the involvement of triplet energy transfer reaction pathway, which was not observed in the reaction with previously reported aminocyclopropenones.

8.
RSC Adv ; 10(52): 31348-31354, 2020 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-35520682

RESUMO

A simple phthalocyanine zinc complex exhibits a visible color change in response to weak external stimuli, i.e., changes in solvent and temperature. Its chromism was attributed to its controlled aggregation via weak interactions between the central metal and peripheral oxygen atoms. In solution, intense absorption and fluorescence bands appeared in both the longer-wavelength and NIR region in non-coordinating solvents, while a simple sharp Q band was observed in coordinating solvents. Variable-temperature absorption spectra and fluorescence lifetime measurements were used to characterize the aggregation-induced absorption and emission in non-coordinating solvents. A selective aggregation-disaggregation process was also observed in thin films of this phthalocyanine zinc complex, and the optical properties of the film depend on the annealing temperature. The changes in the NIR region lead to a sizable visible color change that is recognizable by the naked human eye. The temperature-dependent control of the aggregation process in the thin film was confirmed using operando spectroscopy techniques.

9.
Sci Rep ; 9(1): 16528, 2019 11 11.
Artigo em Inglês | MEDLINE | ID: mdl-31712715

RESUMO

The design of near-IR materials is highly relevant to energy and pharmaceutical sciences due to the high proportion of near-IR irradiation in the solar spectrum and the high penetration of near-IR light in biological samples. Here, we show the one-step synthesis of hexacoordinated ruthenium and iron complexes that exhibit a main absorption band in the near-IR region. For that purpose, novel tridentate ligands were prepared by condensation of two diimines and four cyanoaryl derivatives in the presence of ruthenium and iron template ions. This method was applied to a wide variety of cyanoaryl, diimine, and metal ion combinations. The relationship between the structure and the optical and electrochemical properties in the resulting complexes was examined, and the results demonstrated that these compounds represent novel near-IR materials whose physical properties can be controlled based on rational design guidelines. The intense absorption bands in the 700-900 nm region were assigned to metal-to-ligand charge transfer (MLCT) transitions, which should allow applications in materials with triplet excited states under irradiation with near-IR light.

10.
J Org Chem ; 84(21): 14306-14312, 2019 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-31599149

RESUMO

The synthesis of the first examples of 8-fold α-aryloxy-substituted phthalocyanines is described. 3,6-Diiodophthalonitrile was used as a precursor for a series of 3,6-aryloxy-substituted phthalonitriles, and a lead-mediated macrocyclization was employed to afford the corresponding free-base phthalocyanine complexes. The optical, electrochemical, and aggregation properties of these complexes can be tuned by varying the substituents on the aryloxy groups or by changing the pH value.

12.
Photochem Photobiol Sci ; 18(10): 2397-2410, 2019 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-31347646

RESUMO

Crown ether containing (1,3)pyrenophanes 1-6 were synthesized, and UV absorption and fluorescence spectroscopic studies were carried out to determine their abilities to form complexes with metal and ammonium ions. The fluorescence spectra of 1.0 × 10-5 M solutions of 1, 2, 4 and 6 in 1 : 1 v/v CH2Cl2 : CH3CN were comprised of both monomer and intramolecular excimer emission bands, while only monomer emission bands were present in the fluorescence spectra of 3 and 5. The intensities of the intramolecular excimer emission bands of 1, 2, 4 and 6 in 1 : 1 v/v CH2Cl2 : CH3CN decreased and those of the monomer emission increased in conjunction with the existence of isoemissive points upon the addition of increasing concentrations of various metal perchlorates. The fluorescence spectral changes were dependent on the sizes of crown ether rings and metal ions and, as such, they reflected equilibrium constants for the formation of metal-crown ether complexes. Addition of n-Bu2NH2+PF6- or (PhCH2)2NH2+PF6- to the solutions of the (1,3)pyrenophane linked crown ethers, which brought about similar fluorescence spectral changes, led to the formation of pseudo-rotaxanes as was evidenced by an analysis of 1H NMR spectra and Job's plots. The fluorescence changes of 1 occurred during 5 cycles of repetitive addition and removal of Ba2+. The ratio of intensities of the monomer to the intramolecular excimer emission bands of 1, 2, 4 and 6 increased as the temperature decreased. Based on the experimental observations and the results of DFT calculations, it is concluded that the (1,3)pyrenophanes exist in solution as equilibrium mixtures of anti monomer emitting and syn intramolecular excimer emitting conformers and the equilibrium favors the anti form when the crown ether moieties form complexes with metal or ammonium ions.


Assuntos
Compostos de Amônio/química , Éteres de Coroa/química , Metais/química , Compostos Policíclicos/química , Complexos de Coordenação/química , Entropia , Compostos Policíclicos/síntese química , Espectrometria de Fluorescência , Temperatura
13.
Org Lett ; 21(11): 4101-4105, 2019 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-31117705

RESUMO

A photocatalytic active alkyne generation reaction was developed using cyclopropenone as a starting reagent. Visible light-responsive photocatalysts induced cyclopropenone decarbonylation. The resulting highly reactive alkyne could be used directly, without isolation, for further reactions, such as in a dehydration condensation reaction and alkyne-azide click chemistry.

14.
Chem Commun (Camb) ; 55(51): 7311-7314, 2019 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-31144690

RESUMO

Herein, we report the exceptionally red-shifted absorption of sulfur-substituted silicon(iv) phthalocyanines upon introduction of cationic axial ligands. The Q band was red-shifted to approximately 900 nm with improved hydrophilicity by the combination of peripheral sulfur substituents and axial ammonium ligands. One such phthalocyanine exhibited remarkable photocytotoxicity upon irradiation with NIR light (∼810 nm) in live cells.

15.
Chemistry ; 25(7): 1678-1682, 2019 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-30457173

RESUMO

A robust lead-mediated synthetic procedure for the generation of phthalocyanines substituted with electron-withdrawing groups has been developed. The free-base phthalocyanine and various metal complexes were prepared without discernible degradation of the peripheral electron-withdrawing substituents. Upon irradiation with red light, some of the thus-obtained metal complexes generated high levels of singlet oxygen. In particular, a palladium complex exhibited attractive photostability upon exposure to singlet oxygen as a bleaching agent. The photostability of such complexes that may manifest concomitantly to the generation of high levels of singlet oxygen was attributed to the presence of the electron-withdrawing groups, which results in energetically low-lying highest occupied molecular orbitals.

16.
Yakugaku Zasshi ; 138(6): 731-742, 2018.
Artigo em Japonês | MEDLINE | ID: mdl-29863038

RESUMO

 The combination of several aromatic rings and/or heterocycles can induce novel functions. This phenomenon is observed in porphyrin derivatives, commonly found in hemoglobin, in the active sites of P-450, etc. The ability of these structures to interact strongly with visible light accounts for today's increased interest in the development of rationally designed porphyrinoid-based optical materials. In the pharmaceutical sciences, designing near-IR materials can be a challenge due to the high transparency of near-IR light in biological samples. Phthalocyanines (Pcs) are robust organic dyes that are absorbed in visible light. A theoretical investigation of molecular orbitals of Pcs has revealed that the introduction of a phosphorus(V) atom into a macrocyclic core leads to a narrower highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap. Following these studies, we found that certain types of Pc phosphorus(V) complexes display main absorptions beyond 1000 nm. Additionally, phosphorus(V) complexes with other azaporphyrinoids have been designed and synthesized via a relatively simple procedure. These complexes showed novel optical properties which are potentially useful in the pharmaceutical and material sciences. Furthermore, we have overcome the problem of organic radicals and antiaromatic compounds, which are generally considered to be unstable, by using a combination of serendipitous synthetic methodologies and spectroscopic techniques. These novel azaporphyrin compounds are robust and free from transition metals. They are relatively easy to synthesize and also exhibit predictable properties.


Assuntos
Compostos Azo , Desenho de Fármacos , Raios Infravermelhos , Porfirinas , Compostos Azo/síntese química , Compostos Azo/química , Indóis/química , Isoindóis , Estrutura Molecular , Fósforo , Porfirinas/síntese química , Porfirinas/química , Análise Espectral , Ácido Trifluoracético/química
17.
Phys Chem Chem Phys ; 19(24): 15596-15612, 2017 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-28541354

RESUMO

Azaporphyrinoids, such as phthalocyanines (Pcs), tetraazaporphyrins (TAPs), and tetrabenzotriazacorroles (TBCs), are some of the most well-known and successful artificial dyes and pigments in modern material chemistry. Modifications of the macrocyclic core, periphery, and central element have attracted a great deal of interest in materials sciences due to generation of unique optical and electronic properties. However, the synthesis of most azaporphyrinoids with novel physical properties generally needs long, tedious procedures. On the other hand, the introduction of a phosphorus(v) atom into simple (known) azaporphyrin macrocycles is not necessarily difficult and can generate changes in the structural and optical properties. This paper provides an overview of the recent development of azaporphyrin phosphorus(v) complexes with unique structural and optical properties. Optical properties are discussed based on a combination of experimental absorption spectra, electrochemical properties, and theoretical molecular orbital calculations. These complexes are relatively easy to synthesize, are robust and free from transition metals, and have predictable properties.

18.
Chemistry ; 23(27): 6682-6692, 2017 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-28317197

RESUMO

Detailed electronic, structural, photophysical, and redox studies of a series of meso-pentafluorophenyl-substituted hexaphyrins, namely amethyrin (1), rosarin (2), and rubyrin (3), are described. In prior work, it was found that the electronic states of the antiaromatic hexapyrrolic macrocycle, [24]rosarin 2, could be modified by exposure to several Brønsted acids (e.g., HCl, HBr and HI) to produce either one- and two-electron reduced species, or both. In an effort to gain further insights into the reactivity of hexaphyrins possessing different π-conjugation pathways, the ß-dodecamethyl-substituted [24]amethyrin 1 was prepared and its electronic structure was analyzed along with that of the o-phenylene-bridged [26]rubyrin 3 and rosarin 2 The [4n] and [4n+2] π-conjugated formulations of 2 and 3, respectively, were inferred from steady-state, fs-transient absorption and two photon absorption measurements. Similar photophysical analyses lead to the conclusion that 1 is best considered as nonaromatic or weakly antiaromatic. Magnetic circular dichroism (MCD) spectroscopic analyses of hexaphyrins 1 and 3, as well as comparisons to 2, and theoretical perimeter MO diagram analyses provided support for the electronic assignments. In contrast to what was found for 2, simple protonation of 1 and 3 by halohydric acids did not induce an evident, redox-based change in the electronic structure of the macrocycle.

19.
Dalton Trans ; 45(30): 12041-52, 2016 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-27396712

RESUMO

A series of homoleptic bis{tetrakis(5,7-bis(4-tert-butylphenyl)-6H-1,4-diazepino)[2,3-b,g,l,q]porphyrazinato}lanthanide sandwich complexes [(tBuPh)DzPz]2Ln (Ln = Lu, Er, Dy, Eu, Nd, Ce, La) were prepared and their physicochemical properties were studied to gain insight into the nature of specific interactions in diazepinoporphyrazines. The effect of annulated diazepine moieties and the Ln ionic radius on the properties of the complexes was investigated in comparison with double-decker phthalocyanines. A combination of experimental and theoretical studies revealed the presence of two types of hydrogen bonding interactions in the metal-free porphyrazine and the corresponding sandwich complexes, namely, interligand C-H(ax)N(meso) hydrogen bonding and O-HN(Dz) ligand-water interaction. The interligand hydrogen bonding imparts high stability of the ligand dimer and the double-decker compounds in a reduced state. This work is the first comprehensive investigation into the fundamental understanding of the unusual properties of diazepine-containing macroheterocycles.

20.
Chemistry ; 22(27): 9190-7, 2016 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-27247252

RESUMO

The synthesis, structure, optical and redox properties, and electronic structure of tetrakis(pentafluorophenyl)tetrathiaisophlorin dioxide (12) are reported. Oxidation of tetrakis(pentafluorophenyl)tetrathiaisophlorin (11) with dimethyldioxirane afforded the oxidized product, which was the tetrathiaisophlorin with two thiophene 1-oxide moieties (12). More significant nonplanarity and greater bond length alternation in 12 than those of 11 were observed by X-ray structural analysis. The absorption spectrum of 12 contains two bands at λ=348 and 276 nm, with a weak tail that extends to λ≈650 nm. Analysis of the magnetic circular dichroism spectrum of 12, based on Michl's 4N-perimeter model and molecular orbital calculations, indicate that the broad band at λ=348 nm appears to contain N2 and P2 bands, and 12 is classified as a 4nπ system, similar to 11. The nuclear-independent chemical shift values and (1) H NMR spectroscopy data indicate that 12 has more antiaromatic character than 11.

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