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1.
J Am Chem Soc ; 141(50): 19570-19574, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31736293

RESUMO

Peripherally substituted tetradecaazaheptacene (N14Hp) compounds, exhibiting amphiprotism-coupled emission, have been synthesized. X-ray crystallography reveals a planar acene-like chromophore, and electronic absorption and emission occur in the near-infrared biological transparency window (650-900 nm). The compounds exhibit long-wavelength emission with photoluminescence quantum yields ΦPL up to ∼0.61 at 686 nm, with the monodeprotonated state ΦPL ≈ 0.58 at 712 nm. This unprecedented highly nitrogenous chromophore illustrates the stability and utility of the pyrazinacenes for different applications based on their photophysical properties and chemical structures.

2.
ACS Appl Mater Interfaces ; 8(14): 9059-70, 2016 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-27008198

RESUMO

Pt-CeO(x) nanowire (NW)/C electrocatalysts for the improvement of oxygen reduction reaction (ORR) activity on Pt were prepared by a combined process involving precipitation and coimpregnation. A low, 5 wt % Pt-loaded CeO(x) NW/C electrocatalyst, pretreated by an optimized electrochemical conditioning process, exhibited high ORR activity over a commercially available 20 wt % Pt/C electrocatalyst although the ORR activity observed for a 5 wt % Pt-loaded CeO(x) nanoparticle (NP)/C was similar to that of 20 wt % Pt/C. To investigate the role of a CeO(x) NW promotor on the enhancement of ORR activity on Pt, the Pt-CeO(x) NW interface was characterized by using hard X-ray photoelectron spectroscopy (HXPS), transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS). Microanalytical data obtained by these methods were discussed in relation to atomistic simulation performed on the interface structures. The combined techniques of HXPS, TEM-EELS, and atomistic simulation indicate that the Pt-CeO(x) NW interface in the electrocatalyst contains two different defect clusters: Frenkel defect clusters (i.e., 2Pt(i)(••) - 4O(i)″ - 4V(o)(••) - V(Ce)″″) formed in the surface around the Pt-CeO(x) NW interface and Schottky defect clusters (i.e., (Pt(Ce)″ - 2V(O)(••) - 2Ce(Ce)') and (Pt(Ce)″ - V(O)(••))) which appear in the bulk of the Pt-CeO(x) NW interface similarly to Pt-CeO(x) NP/C. It is concluded that the formation of both Frenkel defect clusters and Schottky defect clusters at the Pt-CeO(x) NW heterointerface contributes to the promotion of ORR activity and permits the use of lower Pt-loadings in these electrocatalysts.

3.
Langmuir ; 29(24): 7186-94, 2013 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-23394576

RESUMO

The development of new methodologies for controlling the organization of quantum materials in multiple dimensions is crucial to the advancement of device fabrication. By using a self-assembly route using selected imidazolium ionic liquids bearing long alkyl chains (C(n)Imida, n = 8, 10, 12) as ligands, we have achieved a tunable assembly of quantum-sized gold nanoparticles. The initial stabilizer of the gold nanoparticles was partially or wholly substituted depending on the concentration and alkyl chain length. π-π interactions between imidazolium rings also promote the generation of spatially controlled aggregates from the nanometer to micrometer size regimes. In particular, in the case of an imidazolium ionic liquid with decyl chains, gold particles assemble into a core-shell spherical superstructure induced by the aggregation of imidazolium ionic liquid molecules during ligand exchange. Conceptually, the assemblies of nanoparticles mimic biological systems and provide strategies for the organization of single-component nanomaterials into functional assemblies for potential applications. Our approach is general and can be applied to other types of nanomaterials for facile manipulation of the assembly processes, permitting an exploration of physicochemical properties as well as technological applications.

4.
Chem Commun (Camb) ; 48(33): 3951-3, 2012 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-22422058

RESUMO

Tetrapyrazinoporphyrazine substituted at its periphery with eight antioxidant 3,5-di-t-butyl-4-hydroxyphenyl groups behaves as a turn-on fluorescent sensor for fluoride anions. Conversely, the precursor antioxidant-substituted 1,2-phthalonitrile was found to act in turn-off mode suggesting that the origin of the phenomenon lies at the phenolate-substituted 1,4-pyrazinyl moiety.

5.
J Nanosci Nanotechnol ; 11(9): 7729-34, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-22097480

RESUMO

Ultrasmall ZnS or PbS nanorods encapsulated in fluid-like soft organic surfactants show excellent miscibility in the nematic liquid crystal (LC ZLI-4792) host resulting in a novel soft matter type blend with enhanced electro-optic properties. The ultranarrow ZnS rods are of wurtzite phase and possess a chemical bipolarity and a net dipole moment. The centrosymmetric ultranarrow PbS rods possess a finite size and shape dependent inherent dipole moment despite their cubic rock-salt structure. When an electric field is applied, the blend aligns along the direction of the field producing a local unidirectional orientation of the rods and LC directors, and defining a unique axis for the system. The local ordering significantly affects the global ordering of the blend allowing a more rapid response of the electro-optic properties. The degree and switching speed of the blends depend upon the magnitude of dipole moments present in the dopant nanorods. We show how a non-mesogenic element designed with preferential crystallographic phase can be introduced within a LC for improvement of the switching properties of the LC blend. These types of unique blends are a model for fundamental conceptual advances in general understanding of interaction behaviour leading consequently to a significant technological advancement for superior device fabrication.

6.
J Am Chem Soc ; 133(40): 16119-26, 2011 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-21875068

RESUMO

Porphyrin derivatives bearing 2,6-di-tert-butylphenol substituents at their 5,15-positions undergo reversible photoredox switching between porphyrin and porphodimethene states as revealed by UV-vis spectroscopy, fluorescence spectroscopy, and X-ray single-crystal analyses. Photoredox interconversion is accompanied by substantial variations in electronic absorption and fluorescence emission spectra and a change of conformation of the tetrapyrrole macrocycle from planar to roof-shaped. Oxidation proceeds only under photoillumination of a dianionic state prepared through deprotonation using fluoride anions. Conversely, photoreduction occurs in the presence of a sacrificial electron donor. Transient absorption spectroscopy and electron spin resonance spectroscopy were applied to investigate the processes in photochemical reaction, and radical intermediates were characterized. That is, photooxidation initially results in a phenol-substituent-centered radical, while the reduction process occurs via a delocalized radical state involving both the macrocycle and 5,15-substituents. Forward and reverse photochemical processes are governed by different chemical mechanisms, giving the important benefit that conversion reactions are completely isolated, leading to better separation of the end states. Furthermore, energy diagrams based on electrochemical analyses (cyclic voltammetry) were used to account for the processes occurring during the photochemical reactions. Our molecular design indicates a simple and versatile method for producing photoredox macrocyclic compounds, which should lead to a new class of advanced functional materials suitable for application in molecular devices and machines.


Assuntos
Fenóis/química , Porfirinas/química , Cristalografia por Raios X , Modelos Moleculares , Oxirredução , Processos Fotoquímicos , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta
7.
Org Biomol Chem ; 9(14): 5005-17, 2011 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-21655575

RESUMO

Acenes have emerged as an important class of organic electronic material. Related heteroatom-substituted compounds, or heteroacenes, introduce an important means for modulating properties and improving materials' stability. In this perspective, we will review the historical origins of the heteroacenes and discuss recent progress in the field of acene and related compounds containing fused 1,4-diazabenzene units, i.e. pyrazine, also known as the 'pyrazinacenes'. We focus not only on the types of materials that have been prepared but also on their chemical and physical properties, including synthetic procedures, electronic properties, self-assembly characteristics, and we also introduce some of the computational studies aimed at understanding the more unusual behaviours of this group of compounds, such as protic tautomerism and aromaticity/antiaromaticity.

8.
J Nanosci Nanotechnol ; 11(1): 1-13, 2011 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-21446402

RESUMO

Nanomaterials have been prepared over a wide range of length scales from nanoscopic objects to bulk structural materials. Recent investigations have been focused on the regulation and control of nanoscopic structures for the modulation of the properties of even macroscopic objects. As an emerging concept, nanoarchitectonics has been proposed as a technology system to be used for arranging nanoscale structural units--i.e., the nanostructure unit as a group of atoms or molecules--in a predesignated configuration. In this review, we summarize recent research on nanomaterials including design, synthesis, fabrication and functionalization based on the nanoarchitectonics concept. Examples are roughly classified according to their dimensionalities: (i) OD nanomaterials (quantum dots, nanocrystals, nanoparticles and nanospheres); (ii) 1D nanomaterials (nanorods, nanowires, nanobelts, nanowhiskers and nanotubes), (iii) 2D nanomaterials (nanosheets, graphene, self-assemble monolayers, Langmuir-Blodgett films, layer-by-layer assemblies and interfacial structures), and (iv) 3D nanomaterials (bulk materials with nanoscale structural control, nanohybrids, nanocomposites and mesoporous materials).

9.
Phys Chem Chem Phys ; 13(11): 4868-76, 2011 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-21225075

RESUMO

Nanotubes of a pentacene derivative, 6,13-bis(1-n-dodecyl)-[a,c,l,n]-tetrabenzo-5,6,7,12,13,14-hexaazapentacene, have been prepared by a hierarchical self-assembly mechanism. The oligoazaacenes 1-3, referred to as pyrazinacenes due to their structures of linearly fused pyrazine heterocycles, can also be considered as two azatriphenylenes fused through a reduced pyrazine ring. Dissolution of 6,13-bis(1-n-dodecyl)-[a,c,l,n]-tetrabenzo-5,6,7,12,13,14-hexaaza pentacene in nearly boiling toluene followed by standing of the solution at room temperature yields self-assembled (sa) pyrazinacene (Pa) nanotubes (NT's), or sa-PaNTs. Self-assembled-PaNTs are formed after initial aggregation of the pyrazinacene giving a 130-nm-wide 2-dimensional tape followed by helical twisting of this tape into a hollow cylindrical form of 150-200 nm diameter which can exceed 10 µm in length. The morphologies of the tape and nanotube structures were investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD) and electron absorption spectroscopy (UV/Vis). The latter indicates that the tubes may be formed by chromophore J-aggregation. Also, high resolution TEM of the tubes reveals that they can be composed of several tapes while powder X-ray diffraction revealed the lamellar structure of the tapes composing the tubes.

10.
Phys Chem Chem Phys ; 13(6): 2145-50, 2011 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-21132187

RESUMO

We present a structural and electronic inspection of reduced pyrazinacenes within the DFT framework. Our analysis provides a clear indication that compounds in which reduced pyrazine rings are well separated from each other are rather stable. Conversely, if the reduced pyrazine rings approach each other or cluster together, the compounds become increasingly unstable. The tautomers analyzed are likely to possess properties suitable for application as proton transport materials due to protic isomerism processes. On the basis of our findings, we propose that protic transport should occur through a concerted proton transfer without involving intramolecular aggregation of the dihydropyrazine groups. Furthermore, the electronic structure analysis shows that this class of compounds can be classified as small bandgap semiconducting materials, possessing even metallic character depending on the tautomeric structure, and with potential nanotechnological applications in molecular electronics and fuel cells.

11.
J Chem Theory Comput ; 6(2): 517-25, 2010 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-26617307

RESUMO

Monoprotic and diprotic NH tautomerism in reduced oligoazaacenes, the pyrazinacenes, was studied by using first principles simulations. Stepwise reductions in the metadynamics-sampled free energy profile were observed during consecutive monoprotic tautomerizations, with energy barriers gradually reducing with increasing proton separation during monoprotic processes. This is accompanied by an increasing contribution from the quinoidal electronic structure, as evidenced by the computed highest occupied molecular orbital (HOMO) structure. An unusual odd-even effect in the free energy profiles is also observed upon changing the length of the pyrazinacene. Calculated HOMO structures reveal an increasing tendency for delocalization of pyrazine lone pairs with an increasing number of ring annelations. The influence of tautomerism on the pyrazine lone pair delocalization was also observed. Tautomers with protons situated centrally on the pyrazinacene backbone are predicted to be more stable due to a combination of (enamine) delocalization and a loss of Clar sextet resonance stabilization in tautomers with protons at terminal pyrazine rings. Experimental evidence suggesting the structure of pyrazinacene tautomers is included and discussed as a support to the calculation.

12.
Sensors (Basel) ; 10(7): 6796-820, 2010.
Artigo em Inglês | MEDLINE | ID: mdl-22163577

RESUMO

Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.


Assuntos
Inteligência Artificial , Estereoisomerismo , Transferência de Energia , Cinética , Microscopia de Tunelamento , Ressonância de Plasmônio de Superfície
13.
J Org Chem ; 74(23): 8914-23, 2009 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-19883040

RESUMO

A series of edge-sharing condensed oligopyrazine analogues of acenes, the pyrazinacenes, were synthesized and characterized. X-ray crystallographic determinations revealed intermolecular interactions that affect the propensity of the molecules to undergo pi-pi stacking. Increasing heteroatom substitution of the acene framework induces shorter intermolecular pi-pi stacking distances (shorter than for graphite) probably due to lower van der Waals radius of nitrogen atoms. Hydrogen bonding is also a determining factor in the case of compounds containing reduced pyrazine rings. Combined electrochemical, electronic absorption, and computational investigations indicate the substantial electron deficiency of the compounds composed of fused pyrazine rings. The pyrazinacenes are expected to be good candidates as materials for organic thin film transistors.

14.
Int J Mol Sci ; 10(5): 1950-66, 2009 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-19564931

RESUMO

Fabrication of nano-sized objects is one of the most important issues in nanoscience and nanotechnology. Soft nanomaterials with flexible properties have been given much attention and can be obtained through bottom-up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and techniques. Among the various functional molecules, dyes have become important materials in certain areas of nanotechnology and their self-assembling behaviors have been actively researched. In this short review, we briefly introduce recent progress in self-assembly of optical molecules and dyes, based mainly on supramolecular concepts. The introduced examples are classified into four categories: self-assembly of (i) low-molecular-weight dyes and (ii) polymeric dyes and dye self-assembly (iii) in nanoscale architectures and (iv) at surfaces.


Assuntos
Corantes/metabolismo , Nanoestruturas/química , Corantes/química , Nanotecnologia/métodos , Fenômenos Ópticos
15.
Langmuir ; 25(15): 8408-13, 2009 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-19281267

RESUMO

The synthesis and morphologies of self-assembled aggregates of novel oligoazapentacene 2 and oligoazaheptacene 3 derivatives are reported. Double nucleophilic substitution on 2,3-dicyano-[h,j]-dibenzo-1,4,5,10-tetrazaanthracene 4 gives the corresponding dihydro-oligoacene derivatives, which were then N-alkylated using n-dodecyl bromide to yield self-assembling acene molecules. 2 and 3 self-assemble in solution, leading to a variety of aggregated structures including rolled-up sheets, foams, and fibrous structures reminiscent of organogels. These structures are of substantial interest because of their potential electronic properties and because individual fibers can be "exfoliated". Structures of the aggregates are discussed. Additionally, the crystal structure of precursor 4 is reported because it gives information regarding the intermolecular interactions (hydrogen bonding and intermolecular stacking) in similar compounds. Crystal data for 4: space group P2(1)/n, a = 9.3164(17) angstroms, b = 7.0649(13) angstroms, c = 23.684(4) angstroms, alpha = 90.00 degrees, beta = 99.945(3) degrees, gamma = 90.00 degrees, and V = 1535.4(5) angstroms3.

16.
Phys Rev E Stat Nonlin Soft Matter Phys ; 71(4 Pt 1): 041706, 2005 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-15903690

RESUMO

The helical structure of uniformly aligned chiral nematic liquid crystals results in a photonic stopband for only one sense of circular polarization. The spectroscopic Stokes polarimeter is used to analyze spontaneous emission in the stopband. Highly polarized photoluminescence is found and the polarization properties vary with the excitation wavelength. Spontaneous emission is enhanced at the stopband edge and this Purcell effect is greater on excitation at wavelengths where the absorption coefficient is low. This is interpreted as greater overlap between the excited molecules and the electrical modal field of the resonant modes at the stopband edge. Photoluminescence detected from the excitation face of the liquid crystal cell is less polarized because of photon tunneling. Fermi's golden rule in conjunction with Stokes vectors is used to model the polarization of emission taking multiple reflections at the interfaces of the cell into account. The discrepancy between the experiment and the theoretical model is interpreted as direct experimental evidence that virtual photons, which originate from zero point fluctuations of quantum space, are randomly polarized.

17.
J Opt Soc Am A Opt Image Sci Vis ; 22(4): 760-6, 2005 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-15839284

RESUMO

A spectroscopic Stokes polarimeter is used to directly measure the linearly, circularly, and randomly polarized components of light obtained on transmission of unpolarized light through thick chiral nematic liquid-crystal cells in the stop band. The Stokes parameters are simulated to fit the experimental data by use of the Berreman 4 x 4 transfer matrix by means of the Jones and Stokes vectors and taking into account multiple reflections at the interfaces of the cell. Excellent agreement is obtained. The transmitted light through a commercial cell is mainly circularly polarized at normal incidence, but a significant linearly polarized component is also observed. The model shows that this results from refractive-index mismatching at the liquid-crystal-alignment-layer interface, but a small linearly polarized component remains even with optimized index matching. An improved device configuration incorporating random defects at the exit boundary of the liquid crystal gives a highly circularly polarized output with virtually no linear or unpolarized components.

18.
Opt Lett ; 29(8): 869-71, 2004 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-15119405

RESUMO

We report a study of a new class of organic semiconductor as an optical gain medium. We demonstrate amplification of violet light by use of stimulated emission in a solution of a first-generation bis-fluorene-cored semiconducting dendrimer. Amplification is also observed in the solid state by means of amplified spontaneous emission in an optically pumped dendrimer planar waveguide. Gains of 36 dB cm(-1) at 420 nm and 26 dB cm(-1) at 390 nm in solution and 350 dB cm(-1) in the solid state are obtained. These results show that semiconducting dendrimers have potential as visible laser and amplifier materials.

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