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1.
J Phys Chem B ; 2021 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-34814686

RESUMO

The photoinduced intramolecular charge separation (CS) and charge recombination (CR) phenomena in a series of donor-bridge-acceptor (D-B-A) molecules are intensively investigated as a means of understanding electron transport through the π-B. Pyrene (Pyr) and triarylamine (TAA) moieties connected via phenylene Bs of various lengths are studied because their CS and CR behaviors can be readily monitored in real time by femtosecond transient absorption (fs-TA) spectroscopy. By combining the steady-state and fs-TA spectroscopic measurements in a variety of solvents together with chemical calculations, the parameters that govern the CS behaviors of these dyads were obtained, such as the solvent effects on free energy and the B-length-dependent electronic coupling (VDA) between D and A. We observed the sharp switch of the CS behavior with the increase of the solvent polarity and B-linker lengths. Furthermore, in the case of the shortest distance between D and A when the electron coupling is sufficiently large, we observed that the CS phenomenon occurs even in low-polar solvents. Upon increasing the length of B, CS occurs only in strong polar solvents. The distance-dependent decay constant of the CS rate is determined as ∼0.53 Å-1, indicating that CS is governed by superexchange tunneling interactions. The CS rate constants are also approximately estimated using Marcus electron transfer theory, and the results imply that the VDA value is the key factor dominating the CS rate, while the facile rotation of the phenylene B is important for modulating the lifetime of the charge-separated state in these D-B-A dyads. These results shed light on the practical strategy for obtaining a high CS efficiency with a long-lived CS state in TAA-B-Pyr derivatives.

2.
Research (Wash D C) ; 2021: 9790705, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34549185

RESUMO

The synthesis of new C-C bonded two-dimensional (2D) covalent organic frameworks (COFs) is highly desirable. Here, a simple but effective synthetic strategy has been developed using an irreversible Brønsted acid-catalyzed aldol cyclotrimerization reaction by virtue of truxene as a linkage. Nonolefin C-C bonded 2D truxene-based covalent organic frameworks (Tru-COFs) were constructed by polymerization of 1,3,5-triindanonebenzene (TDB). The structure formation was confirmed by wide-angle X-ray scattering, Fourier-transform infrared spectroscopy, and solid-state 13C CP/MAS NMR. The results showed that the Tru-COFs were porous (645 m2/g) and chemically stable. Benzyl methylene in conjugated Tru-COFs more effectively produced photoinduced radicals than the model truxene compound. Due to the radical photoresponsiveness, Tru-COFs were efficient catalysts for photocatalytic oxidation of sulfides. We expect that this will provide a new synthetic methodology to obtain C-C bonded functional 2D COFs.

3.
Inorg Chem ; 60(19): 14810-14819, 2021 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-34546744

RESUMO

Three tris-heteroleptic mononuclear Ru(II) complexes with dual fluorescence and phosphorescence-[Ru(dpma)(bpy)(phen)]2+ (12+), [Ru(dpma)(bpy)(dppz)]2+ (22+), and [Ru(dpma)(phen)(dppz)]2+ (32+)-have been designed and used as ratiometric light-response probes for DNA, where dpma is di(pyrid-2-yl)(methyl)-amine, bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline, and dppz is dipyridophenazine, respectively. Single crystals of complex 2(PF6)2 have been obtained and studied by X-ray analysis. The interactions of these complexes with different DNAs are investigated by means of spectroscopic methods, viscosity measurements, and molecular modeling. In the presence of calf thymus DNA, complexes 2(PF6)2 and 3(PF6)2 show the emergence of a new lower-energy phosphorescence emission band; meanwhile, the higher-energy fluorescence emission band is essentially unchanged, functioning as an intrinsic internal reference. These two complexes exhibit stronger preference for calf thymus DNA over single-strand DNA (d(A)16 and d(C)16). In contrast, no binding interaction between 1(PF6)2 and calf thymus DNA is observed. The intrinsic binding constants (Kb) of 2(PF6)2 and 3(PF6)2 with calf thymus DNA are determined to be (1.4 ± 0.4) × 105 and (9.5 ± 0.15) × 104 M-1, respectively. In addition, these spectroscopic results are compared with those of the prototype complex [Ru(bpy)2(dppz)]2+ (42+), and density functional theory and time-dependent density functional theory calculations are employed to elucidate these experimental findings.


Assuntos
Complexos de Coordenação/química , DNA/química , Rutênio/química , Animais , Bovinos , Estrutura Molecular
4.
Angew Chem Int Ed Engl ; 60(30): 16388-16393, 2021 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-34018292

RESUMO

Inorganic cesium lead halide perovskites offer a pathway towards thermally stable photovoltaics. However, moisture-induced phase degradation restricts the application of hole transport layers (HTLs) with hygroscopic dopants. Dopant-free HTLs fail to realize efficient photovoltaics due to severe electrical loss. Herein, we developed an electrical loss management strategy by manipulating poly(3-hexylthiophene) with a small molecule, i.e., SMe-TATPyr. The developed P3HT/SMe-TATPyr HTL shows a three-time increase of carrier mobility owing to breaking the long-range ordering of "edge-on" P3HT and inducing the formation of "face-on" clusters, over 50 % decrease of the perovskite surface defect density, and a reduced voltage loss at the perovskite/HTL interface because of favorable energy level alignment. The CsPbI2 Br perovskite solar cell demonstrates a record-high efficiency of 16.93 % for dopant-free HTL, and superior moisture and thermal stability by maintaining 96 % efficiency at low-humidity condition (10-25 % R. H.) for 1500 hours and over 95 % efficiency after annealing at 85 °C for 1000 hours.

5.
Angew Chem Int Ed Engl ; 60(26): 14595-14600, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-33822449

RESUMO

A simple and general method is presented herein for the in situ preparations of circularly polarized luminescence (CPL)-active microcrystals with a large luminescence dissymmetry factor glum , high fluorescence quantum efficiency (ΦFL ), wide emission color tenability, and well-ordered morphology. The reactions of pyridine-containing achiral molecules 1-7 with chiral camphor sulfonic acid ((±)-CSA) gave crystalline microplates formed by hydrogen bonding interactions between the protonated pyridinium units and the sulfonic anions. The chiral information of CSA are effectively transferred to the microcrystals by hydrogen bonding to afford full-color CPL from deep-blue to red with glum in the order of 10-2 and ΦFL up to 80 %. Moreover, organic microcrystals with high-performance white CPL (ΦFL =46 %; |glum |=0.025) are achieved via the light-harvesting energy transfer between blue and yellow emitters.

6.
Inorg Chem ; 60(9): 6607-6615, 2021 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-33861581

RESUMO

A cationic carbazole-bridged biscyclometalated diplatinum complex 4 has been synthesized and characterized. Single-crystal X-ray analysis demonstrates that complex 4 displays a dimeric structure with noncovalent π-π stacking and unique double Pt-Pt interactions. In aerated dilute CH3CN, complex 4 is characterized by a very weak monomeric yellow emission (λemi = 547 nm; Φ = 0.51%), which is attributed to the triplet intraligand (3LC) excited state mixing with some charge transfer characters. In contrast, under aerated conditions, the dispersion of 4 in a mixed solvent of CH3CN/Et2O (1/9, v/v) or CH3CN/H2O (1/9, v/v) displays intense yellow (λemi = 550 nm; Φ = 35.5%; τ = 11.10 µs) and red emission (λemi = 635 nm; Φ = 14.1%; τ = 7.00 µs), respectively. These aggregation-induced phosphorescent emission enhancements are considered being caused by the oxygen-shielding effect and the molecular rigidification-induced decrease of nonradiative decays in the aggregate state. The morphology and size of the aggregates under these two conditions are examined by scanning electron microscope and dynamic light scattering analysis. The absorption and emission properties of 4 are further rationalized by time-dependent density functional theory calculations on a model compound.

7.
Dalton Trans ; 50(12): 4219-4230, 2021 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-33687405

RESUMO

Three cyclometalated diruthenium complexes bridged by 3,3',5,5'-tetrakis(benzimidazol-2-yl)biphenyl (H-tbibp) and capped with different terminal ligands have been synthesized and examined. In addition, two monoruthenium complexes with H-tbibp have been prepared for the purpose of comparison studies. The degree of Ru-Ru electronic coupling of these diruthenium complexes has been investigated by electrochemical and intervalence charge-transfer (IVCT) analyses. These results suggest that when the same or similar terminal ligands are used, the strength of H-tbibp in mediating the Ru-Ru coupling is enhanced with respect to that of the previously reported bridging ligand 3,3',5,5'-tetrakis(N-methylbenzimidazol-2-yl)biphenyl, but it is slightly inferior to that of the classical bridging ligand 3,3',5,5'-tetrakis(pyrid-2-yl)biphenyl. This trend is also supported by CNS analyses based on the hole-superexchange mechanism. In addition, DFT calculations have been performed to probe the spin density distributions of the singly-oxidized diruthenium complexes with H-tbibp and TDDFT calculations are used to reproduce the IVCT transitions.

8.
Angew Chem Int Ed Engl ; 60(22): 12498-12503, 2021 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-33756014

RESUMO

A Kagome structure covalent organic framework (COF) film with three-state NIR electrochromic properties was designed and synthesized. The COFTPDA-PDA film is composed of hexagonal nanosheets with high crystallinity and has three reversible color states at different applied potentials. It has high absorption spectra changes in the NIR region, ascribed to the strong intervalence charge transfer (IVCT) interaction of the Class III mixed-valence systems of the conjugated triphenylamine species. The film showed sub-second response time (1.3 s for coloring and 0.7 s for bleaching at 1050 nm) and long retention time in the NIR region. COFTPDA-PDA film shows superior NIR electrochromic properties in term of response time and stability, attributed to the highly ordered porous structure and the π-π stacking structure of the COFTPDA-PDA architecture. The COFTPDA-PDA film was applied in mimicking a flip-flop logic gate with optical memory function.

9.
Inorg Chem ; 59(16): 11316-11328, 2020 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-32799462

RESUMO

Molecular packing has an important effect on the photophysical properties of crystalline materials. We demonstrate in this work the modulation of molecular packing and emission properties of microcrystals by minor molecular structural variations. Four platinum ß-diketonate complexes, with two fluoro substituents (1) or one fluoro atom substituted on different positions of the auxiliary phenylpyridine ligand (2-4) have been synthesized. These complexes were used to prepare one-dimensional microcrystals with well-defined shapes and uniform sizes. Although 1-4 display similar emission spectra in the solution state, the corresponding microcrystals display different emission colors from green to yellow and orange. In addition, different temperature-responsive (80-298 K) emission spectral changes have been observed from these microcrystals, including the intensity variation of the locally excited (LE) emission without obvious wavelength shifts, competition between the LE and metal-metal-to-ligand charge-transfer emissions, and the sole wavelength shift of the π-π excimer emissions. These differences in emission properties are rationalized by different molecular packings of these materials, as revealed by single-crystal X-ray analyses.

10.
Chem Commun (Camb) ; 56(14): 2087-2090, 2020 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-31967623

RESUMO

A dual-emissive tris-heteroleptic ruthenium complex is designed, synthesized and applied for the ratiometric photoluminescent detection of amyloid-ß (Aß) aggregation in both steady and transient states. The Aß aggregation is supported by transmission electron microscopy and confocal laser scanning microscopy analysis. In addition, molecular docking calculations have been performed to gain insights into the interaction mode between the ruthenium complex and Aß fibrils.


Assuntos
Peptídeos beta-Amiloides/análise , Complexos de Coordenação/química , Rutênio/química , Complexos de Coordenação/síntese química , Humanos , Simulação de Acoplamento Molecular , Estrutura Molecular , Agregados Proteicos
11.
J Am Chem Soc ; 142(5): 2601-2608, 2020 02 05.
Artigo em Inglês | MEDLINE | ID: mdl-31939661

RESUMO

Singlet oxygen (1O2), as an important active reagent, has found wide applications in photodynamic therapy (PDT), synthetic chemistry, and materials science. Organic conjugated aromatics serving as hosts to capture and release singlet oxygen have been systematically investigated over the last decades. Herein, we present a [6 + 6] organoplatinum(II) metallacycle by using ∼180° dipyridylanthracene donor and ∼120° Pt(II) acceptor as the building blocks, which enables the capture and release of singlet oxygen with relatively high photooxygenation and thermolysis rate constants. The photooxygenation of the metallacycle to the corresponding endoperoxide was performed by sensitized irradiation, and the resulting endoperoxide is stable at room temperature and can be stored under ambient condition over months. Upon simple heating of the neat endoperoxide under inert atmosphere at 120 °C for 4 h, the resulting endoperoxide can be reconverted to the corresponding parent form and singlet oxygen. The photooxygenation and thermolysis products were characterized by NMR spectroscopy and electrospray ionization time-of-flight mass spectrometric analysis. Density functional theory calculations were conducted in order to reveal the frontier molecular orbital interactions and reactivity. This work provides a new material platform for singlet oxygen related promising applications.


Assuntos
Compostos Organometálicos/química , Compostos de Platina/química , Oxigênio Singlete/química , Hidrocarbonetos Policíclicos Aromáticos/química , Análise Espectral/métodos
12.
Research (Wash D C) ; 2020: 6539431, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-33623907

RESUMO

Information encryption and decryption have attracted particular attention; however, the applications are frequently restricted by limited coding capacity due to the indistinguishable broad photoluminescence band of conventional stimuli-responsive fluorescent materials. Here, we present a concept of confidential information encryption with photoresponsive liquid crystal (LC) lasing materials, which were used to fabricate ordered microlaser arrays through a microtemplate-assisted inkjet printing method. LC microlasers exhibit narrow-bandwidth single-mode emissions, and the wavelength of LC microlasers was reversibly modulated based on the optical isomerization of the chiral dopant in LCs. On this basis, we demonstrate phototunable information authentication on LC microlaser arrays using the wavelength of LC microlasers as primary codes. These results provide enlightenment for the implementation of microlaser-based cryptographic primitives for information encryption and anticounterfeiting applications.

13.
J Am Chem Soc ; 141(50): 19831-19838, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31744289

RESUMO

The electrochromic property and device construction of a triphenylamine-based oriented two-dimensional covalent organic framework (2D COF) film on indium tin oxide (ITO) coated glass was reported. The characterization of the 2D COF3PA-TT film revealed that the film was uniform, with good crystallinity, and oriented with its 2D plane parallel to the substrate. For the first time, the electrochromic properties of 2D COF3PA-TT film were studied. 2D COF3PA-TT film on ITO exhibited reversible color transition between deep red and dark brown during redox process. Spectroelectrochemical experiments revealed color changes in the absorption spectra of 2D COF3PA-TT film in the visible and near-infrared regions and showed the characteristics of intervalence charge transfer. The quasi-solid-state electrochromic device was prepared based on the COF3PA-TT film, and it exhibited moderate performance and stability in the near-infrared region.

14.
Chem Commun (Camb) ; 55(89): 13406-13409, 2019 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-31637391

RESUMO

A new small molecular hole-transporting material, 1,3,6,8-tetrakis[N-(p-methoxyphenyl)-N'-(9,9'-dimethyl-9H-fluoren-2-yl)-amino]pyrene (TFAP) was synthesized and applied in CH3NH3PbI3-perovskite solar cells. A best power conversion efficiency of 19.7% with a photovoltage of 1.11 V has been achieved.

15.
Nat Commun ; 10(1): 4599, 2019 10 10.
Artigo em Inglês | MEDLINE | ID: mdl-31601813

RESUMO

Host-guest interactions are of central importance in many biological and chemical processes. However, the investigation of the formation and decomplexation of host-guest systems at the single-molecule level has been a challenging task. Here we show that the single-molecule conductance of organoplatinum(II) metallocycle hosts can be enhanced by an order of magnitude by the incorporation of a C60 guest molecule. Mechanically stretching the metallocycle-C60 junction with a scanning tunneling microscopy break junction technique causes the release of the C60 guest from the metallocycle, and consequently the conductance switches back to the free-host level. Metallocycle hosts with different shapes and cavity sizes show different degrees of flexibility to accommodate the C60 guest in response to mechanical stretching. DFT calculations provide further insights into the electronic structures and charge transport properties of the molecular junctions based on metallocycles and the metallocycle-C60 complexes.


Assuntos
Fulerenos/química , Compostos Organoplatínicos/química , Teoria da Densidade Funcional , Eletrodos , Ouro , Espectroscopia de Ressonância Magnética , Microscopia de Força Atômica , Microscopia de Tunelamento , Espectrofotometria Ultravioleta
16.
Inorg Chem ; 58(19): 13376-13381, 2019 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-31532649

RESUMO

In this work, we present the formation of two open-ended hexagonal-prism tubular macrocycles by the [6 + 12] self-assembly of the symmetric ∼120° organic ligand donor with ∼90° Pt(II) acceptor in a 1:2 ratio. The assembled structures were characterized by multinuclear NMR (1H NMR, 31P{1H} NMR, and 1H-1H COSY NMR), electrospray ionization mass spectrometry (ESI-TOF-MS), traveling wave ion mobility-mass spectrometry (TWIM-MS), and transmission electron microscopy. Molecular modeling was further conducted to get insight into their structured characteristics. We also examined their photophysical properties.

17.
Chem Asian J ; 14(18): 3119-3126, 2019 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-31389657

RESUMO

The bottom-up functionalization of solid surfaces shows increasing importance for a wide range of interdisciplinary applications. Multidentate anchors with more than two contact points can bind to solid surfaces with strong chemisorption, well-defined upright configuration, and tailored functionality. The surface functionalization using multidentate anchors with three (tripodal), four (quadripodal), or more binding points is summarized herein, with a focus on those beyond classical tripodal anchors. In particular, the molecular design on how to achieve multisite interaction between anchor and substrate and the introduction of functional groups to thin films are discussed.

18.
Langmuir ; 35(20): 6571-6577, 2019 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-31002519

RESUMO

Adequate control over the structures of molecular building blocks plays an important role in the fabrication of desired supramolecular nanostructures at interfaces. In this study, the formation of a pure hydrogen-bonding co-assembly supramolecular nanonetwork on a highly oriented pyrolytic graphite surface was demonstrated by means of a scanning tunneling microscope. The thermal annealing process was conducted to monitor the temperature-triggered structural transformation of the self-assembled nanonetwork. On the basis of the single-molecule-level resolution scanning tunneling microscopy images, together with the density functional theory calculations, the formation mechanisms of the formed nanoarrays were proposed. The results have great significance with regard to controlled construction of complex nanostructures on the surface.

19.
J Am Chem Soc ; 141(15): 6157-6161, 2019 04 17.
Artigo em Inglês | MEDLINE | ID: mdl-30945852

RESUMO

Polymorphism and anisotropy are fundamental phenomena of crystalline materials. However, the structure-dependent photoluminescent (PL) anisotropy in polymorphic organic crystals has remained unexplored. Herein, two polymorphic nanocrystals, green-emitting nanorods (PtD-g) and yellow-emitting nanoplates (PtD-y), were obtained from a platinum(II)-ß-diketonate complex. The PtD-y crystals display remarkable PL anisotropy with an anisotropy ratio of up to 0.87 whereas the emission of the PtD-g crystals is nearly unpolarized. The polarization properties are rationalized on the different molecular packing of these crystals. By light-harvesting energy transfer, the PtD-y crystals are successfully used to amplify the emission polarization of a red-emitting platinum acceptor (PtA) doped into the donor crystalline matrix, which is otherwise weakly polarized as pure crystals.

20.
Polymers (Basel) ; 11(1)2019 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-30960057

RESUMO

Two star-shaped multi-triphenylamine derivatives 1 and 2 were prepared, where 2 has an additional phenyl unit between a pyrene core and surrounding triphenylamine units. The oxidative electropolymerization of 1 and 2 occurred smoothly to give thin films of polymers P1 and P2. The electrochemistry and spectroelectrochemistry of P1 and P2 were examined, showing two-step absorption spectral changes in the near-infrared region. The electrochromic properties, including contrast ratio, response time, and cyclic stability of P1 and P2 were investigated and compared. Thin film of P2 displays slightly better electrochromic performance than P1, with a contrast ratio of 45% at 1475 nm being achieved.

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