bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Novel Plasmonic Nanomaterials for Near Infrared Light Energy Conversion
Authors: Teranishi Toshiharu 
Published: February 2020

The structure of nanomaterial determines their individual properties and assembled structures they can form [1,2].Highly efficient photoenergy conversion in heterostructured nanocrystals (HNCs) requires the formation of epitaxial heterointerfaces and band alignment engineering.One of the phases in HNCs should hold the light absorbing ability, such as narrow band gap semiconductor [3-6] and plasmonic material [7-9].Special attention has been given to the HNCs with the combination of plasmonic semiconductor/semiconductor [7-9], where the near infrared plasmon-induced carrier transfer takes place to realize the long-lived charge separation and near infrared light energy conversion into electricity [8] and chemical energy [7,9].
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[6] Sakamoto, M.; Teranishi, T. et al.
Nanoscale
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[7] Lian, Z.; Sakamoto, M.; Teranishi, T.et al.
Nat. Commun.
2018, 9, 2314.
[8] Sakamoto, M.; Teranishi, T.et al.
Nat. Commun., accepted.
[9] Lian, Z.; Sakamoto, M.; Teranishi, T. et al.
J. Am. Chem. Soc., accepted.
High Resolution OLED Using Eco-Friendly Quantum-Dots Functional Color-Filter
Authors: Lee Ji-Eun , Lee Seung-Jae , Kim Seo-Yun , Park Joo-Hyeong , Jung Ui-Hyeon , Sim Tae-hun , Park Jea-Gun 
Published: February 2020

Recently, the quantum-dots enhancement film (QDEF) has been introduced to improve the color gamut for LCD technology. Although this QDEF has been realized approximately zero cross-talk between the main blue-(B-), green-(G-), and red-(R-) light emissions in LCDs to almost zero, it would have a considerable loss (> 10%) in the intensity of light due to the light absorbed in the resin medium and transparent sheets. To solve this undesirable loss of light, the LCD technology has been adopted the QD-functional CF LCD which is simply adding the B, G, and R-QDs directly to the color filters (CFs) in conventional LCDs using a blue back-light-unit (BLU).
Motivated by this idea, we suggest this QDCF technology for organic light emitting diode (OLED) devices. In our research, B-, G-, and R-QD-functional CFs were fabricated by using eco-friendly ZnSe / ZnS and InP-based core/shell structure, showing a high photoluminescence-quantum yield (PL-QY) and a narrow full-width at half-maximum (FWHM) as well as a good flexibility in tuning the suitable PL peak wavelength between emitted from QDs and transmitted from CFs. To make the QD-functional color filter layer, blue, green, and red emitting quantum dots dissolved in hexane of 20wt%. Then they were mixed with the blue, green, and red color filters at a rate of 1 to 1. In order to disperse the QD-functional color filter well, ultra-sonication was performed for 10 minutes. Then, the QD-functional color filter solution was coated on the cleaned substrate using the drop process. After drying for 60 minutes, we analyzed the QD-functional CF structures through photoluminescence and UV-visible spectroscopy. It was confirmed that the B-, G, and R-QDs functional CF OLED exhibited that the PL peak emit at 432, 530, and 621 nm-wavelength with a PL FWHM of 13.4, 39, and 42 nm and a PL-QY of 71, 85, and 75 %, respectively. As a result, the RGB color gamut of the proposed OLED using the fabricated QDs function CFs presented a higher value of 118 % (NTSC) and 88.5% (Rec. 2020) result from the zero cross-talk among PL spectrums of RGB colors (Figure 1). These findings make our study unique and applicable for ultra-super high-resolution OLED and become the cornerstone for trying different types of QDs in QD-functional CFs through a simple, environment-issue free, and cost-effective fabrication process.
We will present in detail the wide RGB gamut characteristics and optical properties of QDCF structures using environmentally friendly ZnSe / ZnS and InP quantum dots in addition to driving OLED.

Figure 1
Electrochemistry of Three-Dimensional Porphyrin Arrays and Related Compounds
Authors: Hiroto Satoru 
Published: February 2020

Three-dimensional π-conjugated molecules have received extensive attention in many chemical research areas due to their interesting structure and unique characteristics. Among these situations, we found that oxidation of aromatic amines was useful for construction of distorted π-conjugated molecules under laboratory conditions. For example, oxidation of beta-amino substituted porphyrins provided three-dimensional porphyrins in excellent yield. In particular, sequential use of amination and oxidation toward 5,10,15,20-tetramesitylporphyrin effectively afforded highly twisted porphyrin oligomers. These oligomers exhibited high solubility in common organic solvent, which is promising for application to solution-processible molecular wire. In addition, we further investigated the substituent effect on the oxidation of beta-aminoporphyrins. We disclosed that dimerization products were varied dependent on meso-aryl substituents. In this presentation, we will show the electrochemical properties of these porphyrin oligomers in order to investigated the effect of distorted conformation on π-electronic network between porphyrin units.
We also found oxidation of N-aryl beta-amino substituted porphyrins produced dehydropyrazine-bridged porphyrin dimers. Recently, we have succeeded in the synthesis of π-extended dihydrophenazine through oxidation of amino-substituted anthracenes. This molecule exhibited conformational change upon electrochemical and chemical redox conditions. Spectral analysis and theoretical calculation revealed that the aromatic and non-aromatic switch of the central dihydropyrazine moiety by two electron oxidation play important role for this electrochemical responsive behaviors. This time, we also prepared π-extended dihydrophenazine based on porphyrins. The structure was clearly elucidated by X-ray diffraction analysis, showing saddle-shape conformation. The electrochemical analysis exhibited irreversible characteristic upon one-electron oxidation and reduction as observed for anthracene derivatives. In this presentation, we will show the synthetic details and electrochemical behaviors of π-extended dihydrophenazines and related porphyrin arrays.
Extension of π Conjugation System By Functionalization of the Beta Position of Porphyrin
Authors: Perera Rajitha , Wang Hong 
Published: February 2020

Porphyrin is a macrocyclic light harvesting molecule that absorbs the light in visible region of the electromagnetic spectrum. Extension of π-conjugation causes the red shifting of the absorbance and adding more fused aromatic rings in to the main macrocycle is a common way to achieve that goal. Heck Coupling reaction can be used to introduce fused aromatic rings in to the β position of porphyrin. π-extended porphyrins possess different and interesting photophysical , Optoelectronic and Physicochemical properties . Aromatic ring fused porphyrins open wide range of applications including in Molecular Rods, Bio sensors, near Infra-red dyes, Photodynamic therapy etc.
In here, we are reporting the use of Heck coupling reaction to synthesis β - extended porphyrin and their red shifted light absorbing properties using its UV-Vis absorption spectrum.
Synthesis, Spectral and Electrochemical Redox Properties of EAA-Appended Porphyrins
Authors: Yadav Inderpal , Sankar Muniappan 
Published: February 2020

Porphyrins having nitro substituents at β-position can act as excellent synthons for further functionalization of porphyrins having wide range of applications [1]. β-Nitro-meso-tetraarylporphyrins can be further functionalized in presence of Michael donor such as active methylene compounds which result in the formation of porphyrins and chlorins depending on reaction conditions and bulkiness of the Michael donor [2-5]. A wide variety of active methylene compounds such as 1,3-dicarbonyls, diketoesters and malonates can undergo Michael addition reactions under mild basic conditions [6]. In this regard, we report the selective synthesis of 2-EAA-5,10,15,20-tetraphenylporphyrins and their metal complexes (Fig. 1a) [7].
All of the synthesized EAA-appended porphyrins exhibited enol tautomeric form in solution predominantly. However, there is no keto-enol tautomerism in it as there is no peak for -CH in 1H NMR spectrum. EAA-appended porphyrins have shown multiple oxidations and reductions in cyclic voltammograms possibly due presence of EAA group on porphyrin ring (Fig. 1b).MTPP(EAA) where M = 2H, Co(II), Ni(II), Cu(II) and Zn(II) exhibited a remarkable red shift (10-15 nm) in the B and Q bands as compared to the corresponding MTPPs, whereas all these porphyrins have bands which are blue-shifted by ∼10-14 nm as compared to their precursor, i.e., MTPP(NO2). In this presentation, we will present the synthesis, spectral and electrochemical redox properties of EAA-appended porphyrins.

Figure 1. (a) Molecular structures of synthesized porphyrins and (b) Cyclic voltammograms (CVs) of CuTPP, CuTPP(NO2) and CuEAA complexes in CH2Cl2 at 298 K.

References

1. Serra, V. I. V.; Pires, S. M. G.; Alonso, C. M. A.; Neves, M. G. P. M. S.; Tome, A. C.; Cavaleiro J. A. S. Heterocycl. Chem.
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2. Chaudhri, N.; Grover, N.; Sankar, M. Chem. 2017, 56, 424.
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4. Chaudhri, N.; Grover, N.; Sankar, M. Chem. 2018, 57, 6658.
5. Chaudhri, N.; Grover, N.; Sankar, M. Chem. 2018, 57, 11349.
6. Shea, K. M.; Jaquinod L.; Smith, K. M. Org. Chem.
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7. Giuntini, F.; Faustino,M. A. F.; Neves, M. G. P. M. S.; Tome, C.; Silva, A. M. S.; Cavaleiro, J. A. S. Tetrahedron
2005, 61, 10454.

Figure 1
Synthesis and Computational Study of Pentacenequinone-Fused Porphyrins with Triply-Split Soret Bands
Authors: Moss Austen , Washburn Spenser , Wang Hong 
Published: February 2020

Porphyrins are one of nature’s most prolific aromatic macrocycles and are one of the most important components of light harvesting in green plants. In pursuit of organic dyes with applications in artificial photosynthesis, porphyrins with broadened and red-shifted UV-Vis spectra are of interest in optimizing the energy obtained from the solar spectrum. Extension of the conjugation of porphyrins through fused rings to the β-positions of the porphyrin induces red-shifted and broadened UV-Visible absorption spectra, but synthesis and characterization of porphyrins with triply-split Soret bands with potential to further enhance the capture of the solar spectrum are unexplored.
Herein there is report of synthesis, crystal structure, and computational study of cross-conjugated β-extended pentacenequinone-fused porphyrins with triply-split Soret bands, which to the best of our knowledge are the first to exhibit such Soret bands. These molecules’ experimental UV-Vis spectrum is compared to computationally derived UV-Vis spectra, and magnetic circular dichroism (MCD) is used to elucidate the electronic transitions that give rise to the triply-split Soret band.

Figure 1
Structural Design of Porphyrins for Binary and Ternary Organic Solar Cells with High Efficiency and Low Energy Loss
Authors: Cuesta Virginia , Vartanian Maida , Sharma Ganesh , de la Cruz Pilar , Langa Fernando 
Published: February 2020

Porphyrin-based molecules have been explored for a long time as the active materials in dye-sensitized solar cells achieving efficiencies as high as 13%. Nevertheless, until the last few years, this family of molecules has been scarcely explored as donor materials in bulk heterojunction (BHJ) organic solar cells (OSCs).
Believing that porphyrin-based molecules should play a more important role in BHJ OSCs we started a few years ago a project in this field using a careful structural optimization. Here I´ll present our last results in this field using porphyrin-based molecules in binary and ternary OSCs, reaching efficiencies close to 10% with low energy loss.
References
1. S. Arrechea, A. Aljarilla, P. de la Cruz, E. Palomares, G. Sharma and F. Langa, Nanoscale, 2016, 8, 17953-17962.
2. G. Morán, S. Arrechea, P. de la Cruz, V. Cuesta, S. Biswas, E. Palomares, G. D. Sharma and F. Langa, J. Mater. Chem. A, 2016, 4, 11009-11022.
3. V. Cuesta, M. Vartanian, P. d. l. Cruz, R. Singhal, G. D. Sharma and F. Langa, J. Mater. Chem. A, 2017, 5, 1057-1065.
4. S. Arrechea, A. Aljarilla, P. de la Cruz, M. K. Singh, G. D. Sharma, F. Langa. J. Mater. Chem. C, 2017, 5, 4742.
5. M. Vartanian, R. Singhal, P. de la Cruz, S. Biswas, G. D. Sharma and F. Langa, ACS Appl. Energy Mater. 2018, 1, 1304.
6. M. Vartanian, P. de la Cruz, F. Langa, S. Biswas, G. D. Sharma. Nanoscale, 2018, 10, 12100.
7. M. Vartanian, R. Singhal, P. de la Cruz, G. D. Sharma and F. Langa. Chem. Commun. 2018, 54, 14144.
Dynamic Molecular Invasion into Multiply Interlocked Catenane Composed of Porphyrins and Phthalocyanine
Authors: Tanaka Kentaro , Yamada Yasuyuki , Ito Ryohei , Ogino Sayaka , Kato Tatsuhisa 
Published: February 2020

Commonly, in molecular inclusion phenomena or molecular recognition processes, flexibility on the molecular size or shape of a host molecule is incompatible with a high affinity of association and accuracy of selectivity. However, if the host has a narrow access for incorporating the guest, the transition process during the complexation requires a higher activation energy. A molecular elevator, which is a molecular machine composed of two planar molecular components joined with more than two interlock linkages, could solve the dilemma through dynamic molecular invasion of a guest molecule into the cage surrounded by the planar components. The movable component with macrocyclic rings fused with a planar core can migrate between two competitive recognition sites along the linear threads attached on the other planar component. However, although the macrocyclic rings are attracted to one of the recognition sites, the planar core with the rings still has the ability to move along the threads. This is because the affinity between the ring and recognition point does not help to anchor the ring at this position, but only increases the probability of the position. Therefore, this flexibility of the interlock linkage satisfies the requirement of the dynamic invasion of a guest molecule. The molecular system permits the invasion of a large guest molecule by expanding the access and stabilizing the host–guest interaction by induced fit based on the interactions between the ring and recognition point.
A multiply interlocked catenane with a novel molecular topology was synthesized; a phthalocyanine bearing four peripheral crown ethers was quadruply interlocked with a cofacial porphyrin dimer bridged with four alkylammonium chains (Figure). The supramolecular conjugate has two nanospaces surrounded by a porphyrin, a phthalocyanine, and four alkyl chains to accommodate guest molecules. Because the phthalocyanine is movable along the alkyl chains, it acts as an adjustable wall, permitting the invasion of large molecules to the nanospaces without spoiling the affinity of the association. The dynamic molecular invasion allowed the intercalation of dianionic porphyrins into both the nanospaces with a high affinity.

Figure 1
Porphyrin-Based Triad with Exceptionally High Magnetic Field Effects (MFE) on Phosphorescence
Authors: Andrianov Dmitry , Vinogradov Sergei 
Published: February 2020

Magnetic control over molecular emissivity presents interests for various fields of technology and medicine. Here, we report experiments exploring magnetic field effects (MFE) on phosphorescence in a new triad, consisting of phosphorescent Pt porphyrin (PtP), rosamine B (RosB) and trialkoxybenzene (TAB), covalently linked together by conductive oligophenylene bridges. Upon photoexcitation the system undergoes two sequential reversible electron transfer processes (ET), generating two radical pairs (RP). The first rate-limiting ET originates in the local PtP triplet state, and it is slightly endergonic, competing with, but not entirely quenching the PtP phosphorescence. The second ET is exergonic, resulting in the formation of the final RP with large inter-radial distance. The RPs recombine either to the ground state (singlet channel) or back to the emissive PtP triplet state (triplet channel). The net distribution over the recombination channels, and hence the phosphorescence decay lifetime and intensity, are governed by the spin dynamics in the RP(s) and, therefore, are sensitive to external magnetic fields.
The triad was found to exhibit remarkably strong positive MFE on phosphorescence at ambient temperatures with the magnitude of ~10% in fields as low as 200 mT. The observed features are characteristic of the hyperfine mechanism, although at higher fields a slight negative MFE was also observed, presumably due to the Δg mechanism. The system was characterized by static and time-resolved optical spectroscopies in the fs, ns and μs-to-ms domains as well as by time-resolved EPR. These studies revealed peculiar dynamics of the system, whereby the initial population of the PtP triplet rapidly equilibrates with the RosB triplet, forming a long-lived triplet reservoir, existing in equilibrium with the RP states. A kinetic model has been developed that allowed us to accurately reproduce the observed charge and energy dynamics of the triad. The model makes it possible to predict how the MFE and the performance of the system can be improved. Overall, this work constitutes an important step forward towards the design of magnetically sensitive luminescent materials.
Thiophene-Fused Expanded Porphyrins with π-System Switching
Authors: Higashino Tomohiro , Imahori Hiroshi 
Published: February 2020

Expanded porphyrins that consist of more than five pyrrole units have attracted much attention because of their unique properties such as a flexible π-conjugation circuit, absorption in the visible to near infrared region, and a variable redox state. Since their optical and photophysical properties can be greatly altered by their π-systems, π-system switching based on expanded porphyrins have attracted much interest.
Recently, we designed expanded porphyrins with dithieno[3,4-b:3',4'-d]thiophene (β-DTT) unit, which can be regarded as an alternative to a thiophene-fused pyrrole unit. The β-DTT unit could yield two types of π-networks, one is a macrocyclic π-network with incorporation of the lone pair of the central sulfur atom, and the other is a cross-conjugated π-network without incorporation of the lone pair. Thus we expected that the β-DTT unit would provide a new class of core-modified and aromatic-fused expanded porphyrins with π-system switching. We synthesized octaphyrins with the β-DTT unit and demonstrated that oxidation of sulfur atoms on the β-DTT unit was able to switch the π-network of octaphyrin from a macrocyclic 36π-electron network to a cross-conjugated network. In addition, we also synthesized hexaphyrins with the β-DTT unit and revealed a unique, unprecedented π-system switching between a Möbius cross-conjugated π-system and a Hückel antiaromatic π-system. Therefore, the β-DTT unit is a new effective motif to realize π-system switching of expanded porphyrins.
Novel Porphyrinoids from α,α-Linked Oligopyrroles
Authors: Martínez-Edo Gabriel , Casado-Aguilera Carlos , Anguera Gonzalo , Kauffmann Brice , Borrell José I. , Borrós Salvador , Sánchez-García David 
Published: February 2020

α,α-linked oligopyrroles play a crucial role in the synthesis of expanded porphyrins. The preparation of macrocycles such as porphycenes, amethyrins or cyclopyrroles is based on the coupling or condensation of the proper functionalized bipyrrole or terpyrrole. Although longer α,α-linked oligopyrroles have been reported, their chemical instability has hampered their use as synthetic building blocks.
Our group have developed a new family of 2,2’-bipyrroles 1 which possesses a remarkable chemical stability ascribed to the presence of two electron withdrawing groups. Bipyrroles 1 can be easily brominated at the α positions allowing their homologation with pyrrole units by means of palladium catalyzed reactions. This strategy has allowed the concise preparation of quaterpyrrole 2 and sexipyrrole 3. In this presentation, the preparation of these oligomers and their use to synthetize new expanded porphyrins will be discussed.

Figure 1
Facile Synthesis of Industrially Scalable and Cost Effective WO3 for Electrochromic Device and Photocatalysis
Authors: Rakibuddin MD , Shinde Mahesh Ashok , Kim Haekyoung 
Published: February 2020

Tungsten trioxide (WO3), an important member of the transition metal oxide family, is a potential candidate for photocatalysis and electrochromic device which have large impact for developing a sustainable environment. The most common chemical strategies for the synthesis of WO3 are the sol−gel and hydrothermal methods, where a tungsten precursor generally a metal tungstate is treated in an acidic environment to generate peroxo−polytungstate acid, followed by heating with capping agents for several hours. However, most of the existing methods are labor intensive, require harsh reaction conditions (high temperature and pressure), have low yields, and also need complex apparatus as well as expensive toxic chemicals. Therefore, the exploration of facile new strategies for the synthesis of WO3 nanostructures continues. Considering the above drawbacks, a simple and low−cost method for the synthesis of WO3 micro–nanostructures by thermal annealing of tungsten powder under ambient conditions is reported. Our strategy is facile, cheap, rapid, and highly reproducible for large–scale production, and the use of toxic precursors or additional capping agents is also eliminated. The as–synthesized WO3 samples are thoroughly characterized. The TEM results show that the size of highly crystalline WO3 particles can be tuned from micro to nano level by simply varying the annealing temperatures. The BET results demonstrate that the surface area and pore size of the synthesized WO3 decreases with increasing annealing temperatures. Furthermore, the WO3 synthesized at 550 °C (WO–550) exhibits higher surface area and pore size, and also excellent photocatalytic activity compared to commercially available WO3. However, among the synthesized WO3 particles, only WO–550 exhibits moderate electrochromic properties. We believe that the synthesis of WO3 nanomaterial by our method could have various industrial applications, and yield an excellent alternative to commercial WO3.
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