Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 20
Filtrar
1.
Small ; : e2406504, 2024 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-39478682

RESUMO

Traditional lighting methods have environmental and efficiency drawbacks. These methods are gradually being overshadowed by light-emitting diodes (LEDs) because of their superior color rendering and energy efficiency. In this study, color-tunable NaBa2(Ba/Sr/Ca)Si2O7F:Eu2+ phosphors are successfully designed by modulating the local crystal field environment through homodominant-group cation substitution, thereby allowing for a spectral shift from blue to bright cyan. Detailed structural analysis of the samples demonstrated the synthesis of high-quality solid-solution materials. A comprehensive examination of the phosphor crystal structure, photoluminescence properties, and fluorescence lifetime reveal that the cyan phosphor possesses a remarkable internal quantum efficiency (IQE = 93%) and low thermal quenching characteristics (I423 K/I303 K = 84%). The results illustrate the critical role of Eu2+-activated cyan phosphors in reducing the spectral gap to attain a natural white-light spectrum, which is indispensable for achieving high color fidelity. The practical application of cyan phosphors in the fabrication of high-performance white LED (WLED) (Ra = 96.8) and fingerprint detection is validated, demonstrating their extensive utility in enhancing visual accuracy and identification.

2.
Inorg Chem ; 63(14): 6362-6369, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38551111

RESUMO

For Tb3+-doped green phosphors, the energy transfer from Ce3+ to Tb3+ can largely enhance the absorption of excitation; however, obtaining phosphors that exhibit both high quantum efficiency and thermal stability continues to pose a significant challenge. Herein, we established a paradigm to achieve novel silicate BaY4Si5O17 (BYSO):Ce3+,Tb3+. The near-ultraviolet light efficiently excites the BYSO:Ce3+ material, causing it to emit light at a wavelength of 408 nm. The photoluminescence of BYSO:0.12Ce3+ exhibits a relatively small Stokes shift and a thermal stability of 89.8% of the 303 K emission intensity at 423 K (89.8%@423 K). The energy transfer (ET) from Ce3+ to Tb3+ ions can be readily constructed in BYSO:Ce3+,Tb3+ utilizing the overlap between the Ce3+ emission and the Tb3+ excitation. The ET efficiency from the Ce3+ to Tb3+ ions reached 83.8% at y = 1.2 and a maximum of 94.6%. Finally, the optimized phosphor BYSO:0.12Ce3+,1.2Tb3+ had an internal quantum efficiency of 94.4% and had excellent thermal stability (96.1%@423 K). Our work pointed out the avenue to novel green phosphors with high efficiency and thermal stability by choosing appropriate host and construct efficient ET.

3.
Inorg Chem ; 63(5): 2655-2662, 2024 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-38247267

RESUMO

In an increasing manner, near-infrared phosphor-converted light-emitting diodes (NIR pc-LEDs) are considered to be exemplary light sources owing to their notable attributes of elevated output power, economical nature, and exceptional portability. NIR phosphors are critical components of NIR pc-LEDs. Herein, we report a novel blue light excitable NIR phosphor CaLu2ZrScAl3O12:Cr3+ (CLZSA:Cr3+) as a crucial and efficient broadband NIR emitter. The CLZSA:Cr3+ phosphor displays an intense NIR broadband emission peaking at 776 nm and with a full width at half-maximum (fwhm) of 140 nm. The designed material also exhibits superior resistance to thermal quenching, as the intensity of emission at 423 K remains at 80% of that at room temperature. The constructed NIR pc-LED device based on CLZSA:Cr3+ demonstrates a high total output power of 68.4 mW at a drive current of 100 mA, along with a high photoelectric conversion efficiency of 23.0%. Impressively, the high-power NIR pc-LEDs are utilized as light sources for remote control and non-invasive detection, resulting in the excellent performance and remarkable achievement.

4.
Inorg Chem ; 62(47): 19341-19349, 2023 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-37955404

RESUMO

The cation-equivalent substitution strategy has the ability to manipulate the luminescence color of phosphors and enhance their overall luminescence performance. A series of novel yellow feldspar-type 3D layered phosphors (Ca1-ySry)4MgAl2Si3O14:xEu2+ were synthesized using a high-temperature solid-state reaction. The solid solution phosphors belong to a tetragonal crystal system with a space group of P4̅21m and cell parameters of a = b = 7.75407-7.91794 Å, c = 5.04299-5.22543 Å, and V = 303.166-327.602 Å3. Under near-ultraviolet (n-UV) excitation, the luminescence color of the phosphor undergoes modulation from yellow-green (530 nm) to blue (467 nm) as the Sr2+ ion substitution ratio increases. This modulation is attributed to the gradual decrease in crystal field splitting energy. Additionally, both the Stokes shift and the full width of the luminescence spectra decrease. Furthermore, there is an increase in the quantum yield (QY) from 45.50 to 60.73%. Finally, the fabricated white-light-emitting diode devices emitted warm white light and achieved high Ra (Ra = 94, 96.6, 92.7) and low correlated color temperature (CCT = 3486, 3430, 3788 K), indicating that the prepared solid solution phosphors can be used as candidate materials for WLED lighting.

5.
Molecules ; 27(22)2022 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-36431800

RESUMO

Non-rare earth doped oxide phosphors with far-red emission have become one of the hot spots of current research due to their low price and excellent physicochemical stability as the red component in white light-emitting diodes (W-LEDs) and plant growth. Herein, we report novel Mn4+-doped La2CaSnO6 and La2MgSnO6 phosphors by high-temperature solid-phase synthesis and analyzed their crystal structures by XRD and Rietveld refinement. Their excitation spectra consist of two distinct excitation bands with the dominant excitation range from 250 to 450 nm, indicating that they possess strong absorption of near-ultraviolet light. Their emission is located around 693 and 708 nm, respectively, and can be absorbed by the photosensitive pigments Pr and Pfr, proving their great potential for plant growth. Finally, the prepared samples were coated with 365 nm UV chips to fabricate far-red LEDs and W-LEDs with low correlation color temperature (CCT = 4958 K/5275 K) and high color rendering index (Ra = 96.4/96.6). Our results indicate that La2CaSnO6:Mn4+ and La2MgSnO6:Mn4+ red phosphors could be used as candidate materials for W-LED lighting and plant growth.


Assuntos
Compostos de Cálcio , Raios Ultravioleta , Óxidos/química , Luz
6.
Small ; 17(41): e2103140, 2021 10.
Artigo em Inglês | MEDLINE | ID: mdl-34510739

RESUMO

The miniaturization of lasers holds promise in ultradense data storage and biosensing, but greater pump power is required to reach the lasing thresholds to overcome increased optical losses with reduced resonant cavity sizes. Here, the whispering galley mode (WGM) of Yb3+ /Tm3+ doped upconversion nanoparticles (UCNPs) coupled with microcavities (≈5 µm) is used to achieve ultralow threshold upconverted lasing at 800 nm with excitation fluences as low as 4 W cm-2 . The continuous-wave (CW) upconverted lasing, with a Q factor on the order of 103 , can remain stable for more than 6 h. In addition, ultralow threshold upconverted microlasers spanning the full visible spectrum from Yb3+ /Er3+ , Yb3+ /Ho3+ , and Yb3+ /Tm3+ doped UCNPs are obtained with the same WGM cavity design. These upconverted microlasers working under low power CW 980 nm laser will enable promising applications in biosensing and imaging.


Assuntos
Elementos da Série dos Lantanídeos , Nanopartículas , Lasers
7.
J Environ Manage ; 213: 255-270, 2018 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-29502011

RESUMO

This paper evaluated the characteristics of interplant water networks along with superstructure models of such networks coordinated with intermediate pools, with the latter being assessed via nonlinear programming tools. To overcome the inherent difficulties associated with nonlinear programming models, a superstructure model was ultimately simplified according to a unidirectional characteristic. A novel step-by-step optimization method was then set forth for this simplified model. And the novel method was then applied to two examples, a single contaminant example from the literature and a multiple contaminants example located in southern China, which could demonstrate the applicability and effectiveness of the proposed method.


Assuntos
Redes Neurais de Computação , Dinâmica não Linear , Abastecimento de Água , China , Modelos Teóricos , Água
8.
ACS Appl Mater Interfaces ; 16(24): 31304-31312, 2024 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-38837961

RESUMO

The pursuit of high-quality phosphors exhibiting swift response to near-ultraviolet (n-UV) excitation, elevated quantum efficiency (QE), superior thermal stability, and impeccable light quality has been a focal point of investigation. In this research, we synthesized a novel K2La2B2O7:Ce3+,Tb3+ (KLBO:Ce3+,Tb3+) color-tunable phosphor that meets these requirements. KLBO:Ce3+ can be stimulated efficiently by the n-UV light and shows an intense blue emission centered at 437 nm. Notably, KLBO:0.04Ce3+ exhibits exceptional internal QE (IQE = 94%) and outstanding thermal stability (I423 K/I303 K = 88%). Optimization of doping compositions enables efficient Ce3+ → Tb3+ energy transfer, resulting in substantial enhancements in QE and thermal stability. Specifically, KLBO:0.04Ce3+,0.28Tb3+ achieves an IQE of 98% and a thermal stability of 97%, higher than those of most phosphors of the same type. White light-emitting diodes fabricated using phosphor samples emit warm white light characterized by high Ra (Ra = 96.6 and 93.4) and low CCT (CCT = 4886 and 4400 K). This study underscores the feasibility of enhancing phosphor QE and thermal stability through energy transfer mechanisms.

9.
Dalton Trans ; 53(14): 6377-6385, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38497415

RESUMO

NIR luminescent materials have garnered widespread attention because of their exceptional properties, with high tissue penetration, low absorption and high signal-to-noise ratio in the field of optical imaging. However, producing nanophosphors with high quantum yields of emitting infrared light with wavelengths above 1000 nm remains a significant challenge. Here, we prepared a nanoscale ZnGa2O4:xCr3+,yNi2+ phosphor with good luminescence performance in near-infrared emission, which was synthesized via a hydrothermal method and subsequent calcination process. By co-doping with Cr3+ and Ni2+, the ZnGa2O4 phosphor shows a strong broadband emission of 1100-1600 nm in the second near-infrared (NIR-II) region, owing to the energy transfer from Cr3+ to Ni2+ with an efficiency up to 90%. Meanwhile, a near-infrared phosphor-conversion LED (NIR pc-LED) device is fabricated based on the ZnGa2O4:0.8%Cr3+,0.4%Ni2+ nanophosphor, which has under 100 mA input current, an output power of 23.99 mW, and a photoelectric conversion efficiency of 7.53%, and can be effectively applied in imaging and non-destructive testing. Additionally, the intensity ratio of INi/ICr of ZnGa2O4:0.8% Cr3+,0.4%Ni2+ with its high sensitivity value of 4.21% K-1 at 453 K under 410 nm excitation, indicates its potential for thermometry application.

10.
Dalton Trans ; 53(16): 6941-6949, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38567552

RESUMO

Phosphors with intrinsic white light emission are of great potential in constructing high-quality white LEDs (WLEDs). In this work, we propose the use of energy transfer from Bi3+ to Eu3+ ions for white light emission. A unique Bi3+-activated phosphor LaGdO3 (LGO):Bi3+ was generated using the conventional high-temperature solid-state process. An energy transfer was established by introducing Eu3+ into the phosphor composition. The emission colour of LGO:Bi3+,Eu3+ phosphors changes from cyan to white to orange-red depending on the Bi3+/Eu3+ doping proportion. The energy transfer between the Bi3+ and Eu3+ ions results from the dipole-dipole interaction. The LGO:Bi3+,Eu3+ phosphors were combined with a near-ultraviolet chip to successfully create a single-component WLED device with a colour-rendering index of 92.4. Our work demonstrates the energy transfer as a route for single-component white light emission and makes LGO:Bi3+,Eu3+ phosphors one of the candidate materials for near-ultraviolet lighting.

11.
Dalton Trans ; 52(47): 17966-17973, 2023 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-37982443

RESUMO

In this work, a series of BaSrGd4O8:xBi3+ blue phosphors was synthesized employing the high-temperature solid-state method. Phase purity of the samples was verified by X-ray diffraction and Rietveld refinement. Time-resolved photoluminescence spectra revealed the existence of two distinct Bi sites. Subsequent optimization of dopant types and doping levels in the batch led to an almost twofold increase in quantum efficiency. The introduction of Eu3+ into the phosphors facilitated the construction of an energy transfer pathway. As the concentration of Eu3+ was increased, the emission color changed from blue to purple and finally to red. In addition, the thermal stability and potential applications of the phosphors were extensively investigated. Finally, two WLED devices were successfully fabricated with color rendering indices of 96.27 and 92.18, and correlated color temperatures of 5198 and 2475 K. This underscores the prospective application of these phosphors in the field of high-quality warm WLEDs.

12.
JACS Au ; 3(3): 860-867, 2023 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-37006769

RESUMO

Phase transition of the polymorphs is critical for controlled synthesis and property modulation of functional materials. Upconversion emissions from an efficient hexagonal sodium rare-earth (RE) fluoride compound, ß-NaREF4, which is generally obtained from the phase transition of the cubic (α-) phase counterpart, are attractive for photonic applications. However, the investigation of the α → ß phase transition of NaREF4 and its effect on the composition and architecture is still preliminary. Herein, we investigated the phase transition with two kinds of α-NaREF4 particles. Instead of a uniform composition, the ß-NaREF4 microcrystals exhibited regionally distributed RE3+ ions, in which the RE3+ with a smaller ionic radius (smaller RE3+) sandwiched the RE3+ with a larger ionic radius (larger RE3+). We unravel that the α-NaREF4 particles transformed to ß-NaREF4 nuclei with no controversial dissolution, and the α → ß phase transition toward NaREF4 microcrystals included nucleation and growth steps. The component-dependent phase transition is corroborated with RE3+ ions from Ho3+ to Lu3+ and multiple sandwiched microcrystals were obtained, in which up to five kinds of RE components were distributed regionally. Moreover, with rational integration of luminescent RE3+ ions, a single particle with multiplexed upconversion emissions in wavelength and lifetime domains is demonstrated, which provides a unique platform for optical multiplexing applications.

13.
Dalton Trans ; 52(35): 12470-12477, 2023 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-37602396

RESUMO

Most commercial phosphor-converted white light-emitting diodes (pc-WLEDs) are manufactured with blue LED chips and yellow-emitting Y3Al5O12:Ce3+ (YAG:Ce3+) garnet phosphor, but the lack of blue-green light in the spectrum results in a low color rendering index (CRI). In this paper, we synthesized Y3ScAl4O12:Ce3+ (YSAG:Ce3+) by replacing Al3+ in YAG:Ce3+ with Sc3+. The introduction of Sc3+ with a larger ionic radius through a cation substitution strategy causes lattice expansion, elongation of the Y-O bond, and ultimately a decrease in Ce3+ 5d level crystal field splitting. As a consequence, the emission spectrum undergoes a blue-shift of 10 nm. Furthermore, the YSAG:Ce3+ phosphor exhibits good thermal stability, and its emission intensity at 423 K is about 58% of that at 303 K. Moreover, the analysis of Eu3+ emission spectra demonstrates that the introduction of Sc3+ resulted in a slight reduction of the dodecahedral lattice symmetry. YSAG:Ce3+ effectively compensates for the lack of the blue-green region, and WLEDs with high color rendering index (90.1), low color temperature (4566 K) and high luminous efficiency (133.59 lm W-1) were prepared using the combination of YSAG:0.08Ce3+, CaAlSiN3:Eu2+ and 450 nm blue chips. These findings indicate that YSAG:Ce3+ garnet phosphor has potential to be used in high quality WLEDs.

14.
Dalton Trans ; 52(21): 7322-7329, 2023 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-37171200

RESUMO

Na2MgScF7 (NMSF) was experimentally obtained for the first time by combining hydrothermal and high-temperature solid-state reactions. X-ray powder diffraction (XRD) combined with Rietveld refinement confirms that NMSF is crystallized in the space group Imma with the cell parameters a = 10.40860(18), b = 7.32804(12) and c = 7.52879(11) Å, α = ß = γ = 90° and V = 574.256(24) Å3. Through doping with Tb3+ or Eu3+ ions, downshifting yellow-green or red emission could be achieved in NMSF-based phosphors, respectively. Upconversion emission could also be designed by doping with Yb3+-Er3+, Yb3+-Tm3+, Yb3+-Ho3+ or Er3+. Moreover, the NMSF:Er3+ phosphor exhibited green upconversion emission upon excitation at 980 nm, and it exhibited red emission upon excitation at 1532 nm. Finally, recognizable patterns were obtained under excitation at 254, 365 and 980 nm, indicating that the as-prepared phosphors can be applied to multicolor anti-counterfeiting. Moreover, our synthesis strategy opens up new avenues for the synthesis of novel fluorides.

15.
Heliyon ; 8(8): e10419, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-36061028

RESUMO

This study focuses on news content related to China and COVID-19 during the COVID-19 pandemic and investigates how media frame, affected the emergence of anti-China sentiments through a case study of Japanese online news discourse. We collected large-scale digital trace data including online news and comments during the COVID-19 pandemic. By employing deep learning-based sentiment classifications, we were able to measure the extent of anti-China sentiments expressed through comments during the pandemic's different phases and on different types of news content. Our results provide empirical evidence that the news media's negative depictions of China and coverage related to political and international relations issues increased as the prevalence of COVID-19 in Japan increased. Importantly, since this coverage can prompt the expression of anti-China sentiment, we argue that the framing used by the media can provide discursive contexts that escalate COVID-19 issues into a broader expression of anti-China sentiment. This study not only identifies the impact of media frames on the expression of anti-China sentiment but also contributes to the development of methods for detecting public opinion and measuring the framing effect with big data and advanced computational tools.

16.
JMIR Med Inform ; 10(3): e31557, 2022 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-35297764

RESUMO

BACKGROUND: The availability of large-scale and fine-grained aggregated mobility data has allowed researchers to observe the dynamics of social distancing behaviors at high spatial and temporal resolutions. Despite the increasing attention paid to this research agenda, limited studies have focused on the demographic factors related to mobility, and the dynamics of social distancing behaviors have not been fully investigated. OBJECTIVE: This study aims to assist in designing and implementing public health policies by exploring how social distancing behaviors varied among various demographic groups over time. METHODS: We combined several data sources, including mobile tracking mobility data and geographical statistics, to estimate the visiting population of entertainment venues across demographic groups, which can be considered the proxy of social distancing behaviors. Next, we used time series analysis methods to investigate how voluntary and policy-induced social distancing behaviors shifted over time across demographic groups. RESULTS: Our findings demonstrate distinct patterns of social distancing behaviors and their dynamics across age groups. On the one hand, although entertainment venues' population comprises mainly individuals aged 20-40 years, a more significant proportion of the youth has adopted social distancing behaviors and complied with policy implementations compared to older age groups. From this perspective, the increasing contribution to infections by the youth should be more likely to be attributed to their number rather than their violation of social distancing behaviors. On the other hand, although risk perception and self-restriction recommendations can induce social distancing behaviors, their impact and effectiveness appear to be largely weakened during Japan's second state of emergency. CONCLUSIONS: This study provides a timely reference for policymakers about the current situation on how different demographic groups adopt social distancing behaviors over time. On the one hand, the age-dependent disparity requires more nuanced and targeted mitigation strategies to increase the intention of elderly individuals to adopt mobility restriction behaviors. On the other hand, considering that the effectiveness of policy implementations requesting social distancing behaviors appears to decline over time, in extreme cases, the government should consider imposing stricter social distancing interventions, as they are necessary to promote social distancing behaviors and mitigate the transmission of COVID-19.

17.
Chem Asian J ; 17(19): e202200639, 2022 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-35932212

RESUMO

Due to the diversity of structure and composition and the unique coordination environment, nitride materials enable the doped activator ions to possess compelling luminescence characteristics, such as rich emission colors, favorable stability and tunable emission spectra. Here, novel SrLuSi4 N7 :Ce3+ ,Tb3+ nitride phosphors were successfully synthesized by a modified carbothermal reduction and nitridation method at atmospheric pressure. SrLuSi4 N7 (SLSN) belongs to hexagonal symmetry, with space group P63 mc, and its crystal structure is composed of the basic building block with corner-sharing [SiN4 ] tetrahedron. Under 365 nm excitation, SLSN:Ce3+ exhibits a broad emission band peaking at 450 nm with a full width at half-maximum (FWHM) of 92 nm and the most forceful intensity obtained at the Ce3+ concentration amount of 0.04. On the basis of the efficient energy transfer, SLSN:Ce3+ ,Tb3+ exhibits color-tunable emission from blue (450 nm) to green (545 nm). Our results indicate that SLSN nitride phosphor is a promising candidate for near-ultraviolet (n-UV) based white LEDs.

18.
J Phys Chem Lett ; 12(46): 11288-11294, 2021 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-34767371

RESUMO

Polarized emission, an inherent characteristic that correlated with structure and morphology, is very sensitive to orientation. For the upconversion (UC) emission of lanthanides, the mechanism of polarization is rarely discussed, and the highly polarized UC emissions are poorly developed. Herein, with the benefit of the strong anisotropic crystal field, well-resolved emissions from lanthanide-doped LiYF4 crystals were studied, and highly polarized UC emissions from Er3+ and Ho3+ were investigated. With multiple sub-energy level transitions, the UC emissions are classified into two sets, with transition dipoles being either parallel or perpendicular to the c-axis of the LiYF4 crystal. An optical three-dimensional orientation sensor was further investigated, in which the in-plane angle is referenced from the orientation of the transition dipoles. In contrast, the out-of-plane angle can be deduced from the change in the degree of polarization. This research deepens our understanding of the polarized photoluminescence, and it opens up an avenue toward unique UC orientation sensors.

19.
Soc Sci Med ; 265: 113517, 2020 11.
Artigo em Inglês | MEDLINE | ID: mdl-33218890

RESUMO

Previous studies have revealed medical, democratic, and political factors altering responses to unexpected infectious diseases. However, few studies have attempted to explore the factors affecting disease infection from a social perspective. Here, we argue that trust, which plays an important role in shaping people' s risk perception toward hazards, can also affect risk perception toward infections from a social perspective. Drawing on the indication that risk perception of diseases helps prevent people from being infected by promoting responsible behaviors, it can be further asserted that trust may alter the infection rate of diseases as a result of risk perception toward infectious diseases. This is an essential point for preventing the spread of infectious diseases and should be demonstrated. To empirically test this prediction, this study uses the COVID-19 outbreak in China as an example and applies an original dataset combining real-time big data, official data, and social survey data from 317 cities in 31 Chinese provinces to demonstrate whether trust influences the infection rate of diseases. Multilevel regression analyses reveal three main results: (1) trust in local government and media helps to reduce the infection rate of diseases; (2) generalized trust promotes a higher rather than lower infection rate; and (3) the effects of different types of trust are either completely or partly mediated by risk perception toward diseases. The theoretical and practical implications of this study provide suggestions for improving the public health system in response to possible infectious diseases.


Assuntos
COVID-19/epidemiologia , COVID-19/psicologia , Confiança , Adolescente , Adulto , Idoso , China/epidemiologia , Feminino , Governo , Humanos , Masculino , Meios de Comunicação de Massa/normas , Pessoa de Meia-Idade , Análise Multinível , Percepção , Medição de Risco , SARS-CoV-2 , Fatores Socioeconômicos , Adulto Jovem
20.
Chem Sci ; 9(22): 4999-5007, 2018 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-29938028

RESUMO

A heterobimetallic complex, (TPFC)Sn-Co(TAP) (TPFC = 5,10,15-tris(pentafluorophenyl)corrole, TAP = 5,10,15,20-tetrakis(p-methoxyphenyl)porphyrin), was synthesized. The complex featured a Sn-Co bond with a bond dissociation enthalpy (BDE) of 30.2 ± 0.9 kcal mol-1 and a bond dissociation Gibbs free energy (BDFE) of 21.0 ± 0.2 kcal mol-1, which underwent homolysis to produce the (TPFC)Sn radical and (TAP)CoII under either heat or visible light irradiation. The novel tin radical (TPFC)Sn, being the first four-coordinate tin radical observed at room temperature, was studied spectroscopically and computationally. (TPFC)Sn-Co(TAP) promoted the oligomerization of aryl alkynes to give the insertion products (TPFC)Sn-(CH[double bond, length as m-dash]C(Ar)) n -Co(TAP) (n = 1, 2, or 3) as well as 1,3,5-triarylbenzenes. Mechanistic studies revealed a radical chain mechanism involving the (TPFC)Sn radical as the key intermediate.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA