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1.
Developing Intense Blue and Magenta Colors in α‐LiZnBO3: The Role of 3d‐Metal Substitution and Coordination 下载免费PDF全文
S. Tamilarasan Prof. Dr. M. L. P. Reddy Prof. Dr. S. Natarajan Prof. Dr. J. Gopalakrishnan 《化学:亚洲杂志》2016,11(22):3234-3240
We describe the synthesis, crystal structures, and optical absorption spectra/colors of 3d‐transition‐metal‐substituted α‐LiZnBO3 derivatives: α‐LiZn1?xMIIxBO3 (MII=CoII (0<x<0.50), NiII (0<x≤0.05), CuII (0<x≤0.10)) and α‐Li1+xZn1?2xMIIIxBO3 (MIII=MnIII (0<x≤0.10), FeIII (0<x≤0.25)). The crystal structure of the host α‐LiZnBO3, which is both disordered and distorted with respect to Li and Zn occupancies and coordination geometries, is largely retained in the derivatives, which gives rise to unique colors (blue for CoII, magenta for NiII, violet for CuII) that could be of significance for the development of new, inexpensive, and environmentally friendly pigment materials, particularly in the case of the blue pigments. Accordingly, this work identifies distorted tetrahedral MO4 (M=Co, Ni, Cu) structural units, with a long M?O bond that results in trigonal bipyramidal geometry, as new chromophores for blue, magenta, and violet colors in a α‐LiZnBO3 host. From the L*a*b* color coordinates, we found that Co‐substituted compounds have an intense blue color that is stronger than that of CoAl2O4 and YIn0.90Mn0.10O3. The near‐infrared (NIR) reflectance spectral studies indicate that these compounds exhibit a moderate IR reflectivity that could be significant for applications as “cool pigments”. 相似文献
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Dipl.‐Chem. Timm Heek Prof. Dr. Frank Würthner Prof. Dr. Rainer Haag 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):10911-10921
Four new water‐soluble polyglycerol‐dendronized perylene, terrylene, and quaterrylene bisimides have been synthesized and characterized with respect to their optical properties in polar organic solvents and water by using UV/Vis and fluorescence spectroscopy. All of these dyes were highly soluble in water, but the size of the chosen polyglycerol dendron was only sufficient to completely suppress dye aggregation for the core‐unsubstituted perylene derivative. Their high solubility in water and their absorption and emission wavelengths up to the NIR region make the core‐unsubstituted perylene and terrylene bisimides ideal candidates for applications in bioimaging, whilst the lack of fluorescence for quaterrylene bisimide in all polar solvents does not warrant further investigation of this chromophore in fluorescence and imaging applications. Likewise, tuning of the emission of rylene bisimides towards longer wavelengths by employing electron‐donating bay substituents is not a promising strategy, owing to the lower fluorescence quantum yields in polar solvents and, in particular, in water. 相似文献
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Dr. Eva M. Barea Dr. Rubén Caballero Leticia López‐Arroyo Dr. Antonio Guerrero Dr. Pilar de la Cruz Prof. Fernando Langa Prof. Juan Bisquert 《Chemphyschem》2011,12(5):961-965
Porphyrins are promising sensitizers for dye solar cells (DSCs) but narrow absorption bands at 400–450 and 500–650 nm limit their light‐harvesting properties. Increasing elongation of the π‐conjugation and loss of symmetry causes broadening and a red‐shift of the absorption bands, which considerably improves the performance of the DSC. Herein we use an oligothienylenevinylene to bridge a Zn‐porphyrin system and the anchoring group of the sensitizer. We separately study the performance of the two basic units: oligothienylenevinylene and Zn‐porphyrin. The combined system provides a three‐fold enhancement of the photocurrent with respect to parent dyes. This is caused by an additional strong absorption in the region 400–650 nm that leads to flat IPCE of 60 %. Theoretical calculations support that the addition of the oligothienylenevinylene unit as a linking bridge creates a charge transfer band that transforms a Zn‐porphyrin dye into a push–pull type system with highly efficient charge injection properties. 相似文献
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Simon Mathew Dr. Martin R. Johnston Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(1):248-253
A covalent dyad composed of a free‐base porphyrin and a perylene diimide ( 1 ) was synthesised and characterised by NMR, HRMS, UV/Vis and fluorometric methods. UV/Vis spectrophotometric analysis indicated a moderate coupling between the components in the ground state. Fluorescence spectroscopy revealed that the emissive properties of the dyad showed that the quantum yield of emission from the porphyrin Soret band increased dramatically and could not be rationalised by a straightforward photoinduced energy (and/or electron) transfer, but rather a coupling of excited states. 相似文献
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Reji Varghese Dr. Hans‐Achim Wagenknecht Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(30):9040-9046
A DNA‐based covalent versus a non‐covalent approach is demonstrated to control the optical, chirooptical and higher order structures of Nile red ( Nr ) aggregation. Dynamic light scattering and TEM studies revealed that in aqueous media Nr ‐modified 2′‐deoxyuridine aggregates through the co‐operative effect of various non‐covalent interactions including the hydrogen bonding ability of the nucleoside and sugar moieties and the π‐stacking tendency of the highly hydrophobic dye. This results in the formation of optically active nanovesicles. A left‐handed helically twisted H‐type packing of the dye is observed in the bilayer of the vesicle as evidenced from the optical and chirooptical studies. On the other hand, a left‐handed helically twisted J‐type packing in vesicles was obtained from a non‐polar solvent (toluene). Even though the primary stacking interaction of the dye aggregates transformed from H→J while going from aqueous to non‐polar media, the induced supramolecular chirality of the aggregates remained the same (left‐handed). Circular dichroism studies of DNA that contained several synthetically incorporated and covalently attached Nr ‐modified nucleosides revealed the formation of helically stacked H‐aggregates of Nr but—in comparison to the noncovalent aggregates—an inversed chirality (right‐handed). This self‐assembly propensity difference can, in principle, be applied to other hydrophobic dyes and chromophores and thus open a DNA‐based approach to modulate the primary stacking interactions and supramolecular chirality of dye aggregates. 相似文献
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Fukuda T Homma S Kobayashi N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5205-5216
The synthesis of a series of zinc phthalocyanines partially phenyl-substituted at the 1-, 4-, 8-, 11-, 15-, 18-, 22-, and/or 25-positions (the so-called alpha-positions) is reported. Macrocycle formation based on 3,6-diphenylphthalonitrile, o-phthalonitrile, and zinc acetate predominantly yielded the near-planar disubstituted complex and opposite tetrasubstituted isomer, while the lithium method yielded the sterically hindered hexasubstituted complex and adjacent tetrasubstituted isomer. All compounds have been characterized by 1H NMR, MALDI-TOF-MS, and elemental analysis methods. In addition, crystal structures have been solved for the di-, hexa-, and octasubstituted complexes and the adjacent tetrasubstituted isomer. DFT geometry optimization calculations predict more highly deformed structures than those observed in the crystals. The packing force of the crystals cannot therefore be ignored, particularly for the less phenyl-substituted derivatives. The crystal structures have revealed that overlap of the phenyl groups causes substantial deformation of the phthalocyanine (Pc) ligands within the crystals, while strong pi-pi stacking in the remainder of the Pc moiety lacking phenyl substituents can suppress the impact of the deformation. Absorption spectra show sizable red shifts of the Q-band with increasing number of phenyl groups. Analysis of the results of absorption spectra and electrochemical measurements reveals that a substantial portion of the red shift is attributable to the ring deformations. Molecular orbital calculations lend further support to this conclusion. A moderately intense absorption band emerging at around 430 nm for highly deformed octaphenyl-substituted zinc Pc can be assigned to the HOMO-->LUMO+3 transition, which is parity-forbidden for planar Pcs, but becomes allowed since the ring deformations remove the center of symmetry. 相似文献
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Silver Quantum Cluster (Ag9)‐Grafted Graphitic Carbon Nitride Nanosheets for Photocatalytic Hydrogen Generation and Dye Degradation 下载免费PDF全文
Dr. Kishore Sridharan Eunyong Jang Jung Hyun Park Prof. Jong‐Ho Kim Prof. Jung‐Ho Lee Prof. Tae Joo Park 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9126-9132
We report the visible‐light photocatalytic properties of a composite system consisting of silver quantum clusters [Ag9(H2MSA)7] (H2MSA=mercaptosuccinic acid) embedded on graphitic carbon nitride nanosheets (AgQCs‐GCN). The composites were prepared through a simple chemical route; their structural, chemical, morphological, and optical properties were characterized by using X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy, transmission electron microscopy, UV/Vis diffuse reflectance spectroscopy, and photoluminescence spectroscopy. Embedment of [Ag9(H2MSA)7] on graphitic carbon nitride nanosheets (GCN) resulted in extended visible‐light absorption through multiple single‐electron transitions in Ag quantum clusters and an effective electronic structure for hydroxyl radical generation, which enabled increased activity in the photocatalytic degradation of methylene blue and methyl orange dye molecules compared with pristine GCN and silver nanoparticle‐grafted GCN (AgNPs‐GCN). Similarly, the amount of hydrogen generated by using AgQCs‐GCN was 1.7 times higher than pristine GCN. However, the rate of hydrogen generated using AgQCs‐GCN was slightly less than that of AgNPs‐GCN because of surface hydroxyl radical formation. The plausible photocatalytic processes are discussed in detail. 相似文献
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Thoresen LH Jiao GS Haaland WC Metzker ML Burgess K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(19):4603-4610
Syntheses of a unique set of energy transfer dye labeled nucleoside triphosphates, compounds 1-3, are described. Attempts to prepare these compounds were only successful if the triphosphorylation reaction was performed before coupling the dye to the nucleobase, and not the other way around. Compounds were prepared as both the 2'-deoxy (a) and 2',3'-dideoxy- (b) forms. They feature progressively longer rigid conjugated linkers connecting the nucleobase and the hydroxyxanthone moiety. UV spectra of the parent nucleosides 12-14 show that as the length of the linker increases so does the absorption of the donor in the 320-330 nm region, but with relatively little red-shift of the maxima. Fluorescence spectra of the same compounds show that radiation in the 320-330 nm region results in predominant emission from the fluorescein. When the linker is irradiated at 320 nm, the only significant emission observed corresponds to the hydroxyxanthone part of the molecules at 520 nm; this corresponds to an effective Stokes' shift of 200 nm. As the absorption at 320-330 nm by the linker increases with length, so does the intensity of the fluorescein emission. A gel assay was used to gauge relative incorporation efficiencies of compounds 1-3, dTTP, ddTTP, and 6-TAMRA-ddTTP. Throughout, the thermostable polymerase TaqFS was used, as it is the one most widely applied in high throughput DNA sequencing. This assay showed that only compounds 3 were incorporated efficiently; these have the longest linkers. Of these, the 2'-deoxy nucleoside 3 a was incorporated and did not prevent the polymerase from extending the chain further. The 2',3'-dideoxy nucleoside 3 b was incorporated only about 430 times less efficiently than ddTTP under the same conditions, and caused chain termination. The implications of these studies on modified sequencing protocols are discussed. 相似文献
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The structure of trans‐[Cr(tn)2Br2]ClO4 (tn = propane‐1, 3‐diamine) has been determined by a single‐crystal X‐ray diffraction study at 100 K. The complex crystallizes in the space group P$\bar{1}$ of the triclinic system with two mononuclear formula units in a cell of dimensions a = 6.8220(4), b = 8.86199(9), c = 12.6644(8) Å and α = 77.859(7)°, β = 81.765(6)°, and γ = 77.764(7)°. The chromium atom is in a slightly distorted octahedral environment coordinated by four nitrogen atoms of two tn ligands and two bromine atoms in trans positions. The two six‐membered chelate rings in the complex cations are oriented in an anti chair‐chair conformation with respect to each other. The mean Cr–N(tn) and Cr–Br bonds are 2.093(3) and 2.4681(4) Å, respectively. The crystal packing is stabilized by hydrogen bonds. The infrared and electronic absorption spectral properties are consistent with the result of X‐ray crystallography. It is confirmed that the nitrogen atoms of the tn ligand are strong σ‐donors, but the bromido ligands have weak σ‐ and π‐donor properties toward the chromium(III) ion. 相似文献
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Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H‐ZSM‐5 Crystals during Alcohol‐to‐Hydrocarbon Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy 下载免费PDF全文
Dr. Emily C. Nordvang Dr. Elena Borodina Dr. Javier Ruiz‐Martínez Prof. Dr. Rasmus Fehrmann Prof. Dr. Bert M. Weckhuysen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17324-17335
The catalytic activity of large zeolite H‐ZSM‐5 crystals in methanol (MTO) and ethanol‐to‐olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro‐spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H‐ZSM‐5 crystals, which are transformed into more poly‐aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H‐ZSM‐5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results. 相似文献
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Dyes in Liquid Crystals: Experimental and Computational Studies of a Guest–Host System Based on a Combined DFT and MD Approach 下载免费PDF全文
Mark T. Sims Dr. Laurence C. Abbott Dr. Stephen J. Cowling Prof. Dr. John W. Goodby Dr. John N. Moore 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(28):10123-10130
Practical applications of guest–host liquid crystal systems are critically dependent on the alignment of the guest species within the liquid crystal host. UV/Vis absorption spectroscopy shows that the 1,5‐dihydroxy‐2,6‐bis‐(4‐propylphenyl)‐9,10‐anthraquinone dye aligns within the E7 nematic host, giving an experimental dichroic ratio of 9.40 and dye order parameter of 0.74. This alignment was modelled by using a combination of density functional theory (DFT) and molecular dynamics (MD) computational approaches that do not require the input of experimental data. Time‐dependent DFT calculations show that the electronic transition dipole moment is highly aligned with the long molecular axis of the dye. Fully atomistic MD simulations show that the long axis of the dye is less highly aligned within the E7 host, indicating that this contribution limits the overall dye alignment and, thereby, the potential practical applications of this particular system. Importantly, this study demonstrates an experimental and combined DFT and MD computational approach that may be applied generally to guest–host systems, providing a potential route to their rational design. 相似文献
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A perylenetetracarboxylic diimide hexamer (6PDI) and a dimer (2PDI) linked with the same hexaphenylbenzene group were prepared, and the structures were fully characterized by 1H NMR spectroscopy, mass spectrometry, and elemental analysis. Due to the similar molecular structure of these two compounds, similar interactions between/among the PDI subunits as well as similar photophysical properties are expected. However, the stationary UV/Vis absorption spectra reveal that the interactions among/between the PDI subunits in 6PDI are significantly stronger than those in 2PDI. This can be attributed to blocked rotation along the long axis of the PDI subunits in 6PDI due to steric hindrance of the two neighboring PDI subunits. The stronger interactions among the PDI subunits in 6PDI lead to long‐wavelength emission, which can be assigned to “excimer‐like” excited states. A similar conclusion can also be deduced from the fluorescence quantum yields and the fluorescence lifetimes. Electrochemical studies revealed that interactions between/among the PDI subunits in both 2PDI and 6PDI are still in the range of weak interactions. Ultrafast transient anisotropy decay dynamics revealed that excitation delocalization between the PDI subunits within 2PDI and 6PDI is quick and efficient. More interestingly, delocalization is faster in 6PDI than in 2PDI, probably because of the stronger interactions among the PDI subunits in the former. 相似文献
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A new 3D MnII metal‐organic framework compound {Mn(phen)(dcbp)}n (H2dcbp = 4,4‐dicarboxy‐2,2′‐bipyridine, phen = 1,10‐phenanthroline) was isolated under hydrothermal conditions and structurally characterized. In the compound, the dcbp ligand is deprotonated to give a neutral species (metal:ligand with 1:1 stoichiometry). Along the c axis, the neighboring MnII ions are linked by two carboxylate bridges in µ2‐coordinating mode to generate a 1D zigzag chain, and these chains are interlinked by dicarboxylate groups of long dcbp ligands to generate a 3D (4,4)‐connected structure with the (42.84) net topology. IR and UV/Vis spectroscopy and variable temperature magnetic susceptibility measurements were made, which indicated weak antiferromagnetic interactions between the MnII ions of the compound. 相似文献
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Platinum trans‐Bis(borirene) Complexes Displaying Coplanarity and Communication Across a Platinum Metal Center 下载免费PDF全文
Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Rian D. Dewhurst Hauke Kelch Bret B. Macha Dr. Krzysztof Radacki Dr. Alfredo Vargas Dr. Qing Ye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2377-2386
Ambient‐temperature photolysis of the aminoborylene complex [(OC)5Cr?B?N(SiMe3)2] in the presence of a series of trans‐bis(alkynyl)platinum(II) precursors of the type trans‐[Pt(CCAr)2(PEt3)2] (Ar=Ph, p‐C6H4OMe, and p‐C6H4CF3) successfully leads to twofold transfer of the borylene moiety [ : B?N(SiMe3)2] onto the alkyne functionalities. The alkynyl precursors and resultant bis(borirene)platinum(II) complexes formed are of the type trans‐[Pt(B{?N(SiMe3)2}C?CAr)2(PEt3)2] (Ar=Ph, p‐C6H4OMe, and p‐C6H4CF3). These species have all been successfully characterized by NMR, IR, and UV/Vis spectroscopy as well as by elemental analysis. Single‐crystal X‐ray diffraction has verified that these trans‐bis(borirene)platinum(II) complexes display coplanarity between the twin three‐membered rings across the platinum core in the solid state and stand as the first examples of coplanar conformations of twin borirene systems. These complexes were modeled using density functional theory (DFT), providing information helpful in determining the ability of the transition metal core to interact with each individual borirene ring system and allowing for the observed coplanarity of these rings in the solid state. This proposed transition metal interaction with the twin borirene systems is manifested in the electronic characterization of these borirene species, which display divergent photophysical UV/Vis spectroscopic profiles compared to a previously published mono(borirene)platinum(II) complex. 相似文献
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Changzhun Shao Dr. Matthias Grüne Dr. Matthias Stolte Prof. Dr. Frank Würthner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(43):13665-13677
A novel perylene bisimide (PBI) dye bearing one solubilizing dialkoxybenzyl and one bulky 2,5‐di‐tert‐butylphenyl substituent was synthesized and its aggregation behavior was analyzed by NMR and UV/Vis spectroscopy in various chloroform/methylcyclohexane (MCH) solvent mixtures. In the presence of no less than 10 vol % chloroform, exclusive self‐assembly of this PBI dye into π‐stacked dimers was unambiguously confirmed by means of both concentration‐dependent 1H NMR and UV/Vis spectroscopic experiments. Based on ROESY NMR, a well‐defined π‐stacked dimer structure was determined and further corroborated by molecular modeling studies. By varying the solvent composition of chloroform and MCH, the solvent effects on the Gibbs free energy of PBI dimerization were elucidated and showed a pronounced nonlinearity between lower and higher MCH contents. This observation could be related to a further growth process of dimers into larger aggregates that occurs in the absence of chloroform, which is required to solvate the aromatic π surfaces. With the help of a single‐crystal structure analysis for a related PBI dye, a structural model could be derived for the extended aggregates that are still composed of defined π–π‐stacked PBI dimer entities. 相似文献