bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rigid and Flexible Bis-Porphyrinic Tweezers: Efficient Molecular Recognition of Bidentate Bases.
Authors: Rein Regis , Solladie Nathalie 
Published: February 2020

Increasing efforts are devoted to the synthesis of cofacial bis-porphyrinic tweezers able to complex various bidentate guests through axial coordination of the Zn(II) porphyrins by the two nitrogen atoms. Elaboration of rigid receptors appeared up to now as the ideal way to pre-organize a bis-porphyrinic cavity and increase the stability of the formed host/guest complexes. However, the choice of using rigid spacer to attach the two porphyrins together may cost a lot as far as solubility and stability are concerned. The synthetic pathways necessary to achieve the synthesis of rigid systems are frequently long and tedious. We report here the synthesis and studies of new flexible bis-porphyrinic tweezers bearing uridine as linkers and offering pre-organized cavities able to welcome bidentate guests with extremely high association constants.
As part of our studies concerning complexation of bidentate Lewis bases by bis-porphyrinic tweezers, we have synthesized two new bis-porphyrins bearing a flexible nucleosidic linker. Both uridine and 2’-deoxyuridine spacers were chosen on account of some observations we made a few years ago on the unexpected blocked conformations adopted by a pentaporphyrin consisting of four Zn(II) porphyrins attached to a central free-base porphyrin by four nucleosidic linkers. Since we observed no such blocked conformations in other flexible pentaporphyrins, we thought this might be due to the nucleosidic nature of the linkers. We thus synthesized two dimers, which differ by the attachment positions of the two porphyrins.
The ability of these two tweezers to accomodate guests was investigated through ligand binding studies carried out in dichloromethane with DABCO as bidentate base. The complexation of DABCO by these dimers was monitored by UV-visible spectrophotometric titration in CH2Cl2. The binding constants between these two tweezers and DABCO were calculated from UV-visible spectroscopic data. These association constants are unexpectedly increased by more than one order of magnitude as compared to the association constants of the same bidentate ligand with a reference Zn(II) mono-porphyrin. This enhanced stability of the complexes may be ascribed to a pre-organization of the bis-porphyrinic tweezers forming a cavity, and provides convincing evidence that the bidentate base is inserted into the cavity of the dimers via host/guest interactions.
We demonstrated that similar association constants can be obtained with flexible tweezers bearing uridine as linker and rigid tweezers. However, the stability of these flexible complexes isn’t as convincing as for our rigid tweezers bearing a tris-anthracenic spacer since the addition of an excess of DABCO destroys all the flexible complexes.
Molecular modelling of one of the flexible tweezers and its 1/1 complex with DABCO is represented below, as well as our rigid tweezers bearing a tris-anthracenic spacer.

Acknowledgements

This work was supported by the CNRS and the French Ministry of Research.

Figure 1
Gas Phase Synthesis and Deposition of Directly Fused Porphyrin Tapes: Reaction Mechanism and Central Metal Ion Effect.
Authors: Bengasi Giuseppe , Baba Kamal , Back Oliver , De Castro Olivier , Frache Gilles , Heinze Katja , Boscher Nicolas D. 
Published: February 2020

The formation of directly fused porphyrin tapes attracted the interest of the scientific community because of their electronic and optical properties such as extremely low bandgap, NIR and two photon absorption. The synthesis of these compounds is tedious because of their low solubility and require the introduction of solubilizing substituents adding further synthetic efforts.[1] Moreover, these materials are hard to process and integrate into device while the solubilizing substituents hinder the π­-π interactions affecting the properties of the resulting materials.[1],[2] These drawbacks were circumvented with the oxidative Chemical Vapour Deposition (oCVD) of phenyl meso-substituted porphyrins, which allowed to achieve in a single step the synthesis, deposition and doping of polymeric fused porphyrins tapes thin films from commercially available chemicals.[2] Our approach allows the deposition of patterned films and is compatible with sensitive substrates such as paper or polymers (Figure 1a). Using Ni(II) 5,15–(diphenyl) porphyrin (NiDPP), 5,10,15–(triphenyl) porphyrin (NiP3P) and 5,10,15,20–(tetraphenyl) porphyrin (NiTPP), we elucidate the reaction active sites, the side reactions (Figure 1b) and the differences to solution based approaches via high resolution mass spectrometry, UV-Vis-NIR spectroscopy, electron paramagnetic resonance (EPR) and Density Functional Theory (DFT). We also investigate the effect of the central metal ion on the direct fusion reaction of Fe(III)Cl, Co(II), Ni(II), Cu(II), Pd(II), H2 and Zn(II), 5,15–(diphenyl) porphyrins in oCVD. Furthermore, the electrical, electronic and morphological properties of the prepared thin films were thoroughly investigated by means of X-ray Photoelectron Spectroscopy (XPS), Helium Ion Microscopy (HIM) and Conductive Atomic Force Microscopy (C-AFM).
[1] T. Tanaka, A. Osuka – Conjugated porphyrin arrays: synthesis, properties and applications for functional materials – Chem Soc Rev.
2015, 44, 943.
[2] G. Bengasi, K. Baba, G. Frache, P. Gratia, K. Heinze, N. D. Boscher – Conductive Fused Porphyrin Tapes on Sensitive Substrates by a Chemical Vapor Deposition Approach – Angew. Chem. Int. Ed.
2018, DOI: 10.1002/anie.201814034.
Figure 1) a) The chemical vapour deposition reaction of NiDPP and FeCl3 yields a homogeneous and conductive coating also on sensitive and bendable substrates which evidences the suitability for modern optoelectronic devices. b) Reaction schemes for the CVD reaction of NiDPP and FeCl3 and side reactions observed during the deposition (chlorination, cyclization of the phenyl ring).

Figure 1
Molecular Design of Metal Phthalocyanines with Strong Electron-Donating Substituents for Perovskite Solar Cells
Authors: Zanotti Gloria 
Published: February 2020

Perovskite solar cells have recently revolutionized the field of the emerging photovoltaic technologies, showing an impressive evolution in the last ten years jumping from an initial 3.8%1 to a 22.1%2 certified efficiency. Nonethless, there are still ongoing challenges to face in order to foresee their commercialization, some of which are related to the use of the expensive Spiro-OMeTAD as hole transport material (HTM) and to the active layer morphology, whose inhomogeneity can promote low-resistance shunting paths, loss of light absorption and perovskite degradation in the solar cells, undermining their photovoltaic performances and stability during time. Phthalocyanines are macrocyclic aromatic compounds that can potentially address both the issues: their p-type semiconducting properties make them appealing materials as hole transporters and at the state of the art, they have scored very high efficiencies3-4 in perovskite-based devices. Furthermore, they are potentially effective as surface passivants, reducing the active layer pinholes and increasing both stability and performances of the corresponding devices, because of their excellent thermal and chemical stability, hydrophobic carbon-based core and good processability within the solar cells.
With the aim of addressing both the issues individually, in this contribution we will discuss our synthetic strategies for the preparation of several metal phthalocyanines, conveniently functionalized with strong electron-donating substituents and suitable functional groups, along with our first results of their implementation in perovskite-based devices.
References:

Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Am.
Chem. Soc.
2009, 131(17), 6050-6051.

Yang, W. S.; Park, B.-W-; Jung, E. H.; Jeon, N. J.; Kim, Y. C.; Lee, D. U.; Shin, S. S.; Seo, J.; Kim, E. K.; Noh, J. H.; Seok, S. I. Science, 2017, 356, 1376-1379.

Cho, K. T.; Trukhina, O.; Roldán-Carmona, C.; Ince, M.; Gratia, P.; Grancini, G.; Gao, P.; Marszalek, T.; Pisula, W.; Reddy, P. Y.; Torres, T.; Nazeeruddin, M. K.
Energy Mater.
2017, 1601733.

Duong, T. et al., ACS Energy Lett., 2018, 3(10), 2441–2448.
Subphthalocyanine Fused Dimer and Subphthalocyanines Conjugates
Authors: Zango German , Mariñas Víctor , Fernandez-Vera Oscar , Gallego Lucia , Lavarda Giulia , Medina Diana Paola , Martínez-Díaz M. Victoria , Torres Tomas 
Published: February 2020

An approach for employing SubPcs and SubPc fused dimers [1] as active units in molecular recognition of fullerenes and artificial photosynthetic systems has been developed. Thus, the preparation of multi-SubPc systems constituted by SubPc and SubPc fused dimer units connected by their mutual axial positions has been explored. For this purpose, a series of SubPcs and SubPc dimers bearing different conjugated spacers linked by alkyne bonds to the SubPc or SubPc dimer boron atoms have been synthesized. Two multi-SubPc hybrids comprised of a perfluorinated SubPc fused dimer (syn or anti topoisomer) axially functionalized with unsymmetrical octylthio-substituted SubPcs linked through their periphery by ethynyl linkers to the boron atoms of the dimer have been prepared. Electrochemical and steady state photophysical studies of the syn- hybrid suggest the existence of an electron transfer process from SubPc units to photoexcited SubPc dimer to generate a (SubPc•+-SubPc Dimer•-) radical pair.
Furthermore, the position that the two axial SubPc units acquire in this assembly gives rise to unique supramolecular recognition sites suitable for the complexation of fullerenes. Thus, the binding ability of this hybrid towards different fullerene derivatives, namely C60
, C70
, C60-PCBM and C70-PCBM, has been analyzed through UV-vis absorption, fluorescence and NMR titrations. It has been demonstrated that syn-compounds display a unique fullerene complexation mode. Initially, the formation of a 1:1 supramolecular complex, where the axial octylthio-substituted SubPcs embraces a guest molecule with remarkable association constants of around 106 - 104 M-1, is observed. The spatially-defined cavity generated by the rigid and short alkynyl linkers shows a higher affinity for the bigger fullerene derivatives. Then, a secondary supramolecular interaction between the perfluorinated SubPc syn dimer unit and another fullerene molecule has been detected and quantified, with significant binding constants of 104-103 M-1 that depend on the size and the host-guest electrostatic interactions, leading to the formation of the final 1:2 supramolecular ensemble [2].
[1] C. G. Claessens, D. González-Rodríguez, M. S. Rodríguez-Morgade, A. Medina, T. Torres, Chem. Rev.
2014,
114, 2192–2277.
[2] G. Zango, V. Mariñas, M. V. Martínez-Díaz, D. Guldi, T. Torres, in preparation
(Invited) Advanced Nanostructured Electrode Materials for Lithium-Sulfur Batteries
Authors: Chen Zhongwei 
Published: February 2020

Advanced battery technology plays key roles in pursuit of sustainable energy future by electrifying the transportation fleet and converting/storing the intermittent green energy source in grid scale. Among the candidates, lithium-sulfur (Li-S) battery has risen up as a particularly promising successor to the currently dominating lithium-ion batteries due to its intriguingly high energy density and cost effectiveness. However, the practical implementation of Li-S battery can be achievable only when several critical problems are well addressed, which involve the insulting nature of cathode materials, the unruly polysulfide shuttling behavior, low efficiency of metallic lithium redox reactions, etc. These bugbears have been haunting the Li-S system and obstructing its access to practically high capacity and long lifespan.
Targeting at these problems, we have long been committed to pursuing high-efficiency Li-S electrochemistry with extensive research interests in multiple battery ingredients. Following the two strategic emphasis on conduction properties and sulfur confinement, a series of functional host materials with delicate nano-/micro-structures has been successfully developed to fulfill fast and durable sulfur electrochemistry, which enables high sulfur loading and minimum electrolyte with achievable energy density that meets the commercial benchmark. Beyond that, targeted surface functionalization has been dedicated on separator to regulate the diffusion behavior of polysulfide, while host strategy with rationally-designed architecture has been also employed in lithium anode to suppress the dendrite formation and enhance the redox reversibility. Through the multi-sectional improvements, we are aiming at the establishment of an interoperable mechanism at a system level to promote the fundamental understanding as well as the practical electrochemical performance of Li-S battery for future commercialization.
(Invited) Nano Carbon and Polymeric Materials for Energy Conversion and Storage
Authors: Chen Yongsheng 
Published: February 2020

Green energy technologies have been highly demanded for a sustainable development. In this talk, our recent studies for the electricity conversion/storage using nano carbon and polymeric materials will be presented. These will include the material design, synthesis, and device fabrication, targeting for high energy efficiency and understanding the mechanism using simpler or cheap materials.
Recent five references:

"Polymeric Graphene Bulk Materials with a 3D Cross-Linked Monolithic Graphene Network", Wangqiao Chen, Peishuang Xiao, Honghui Chen, Hongtao Zhang, Qichun Zhang, and Yongsheng Chen*,
Mater
., 2018, 1802403.

"Nonfullerene Tandem Organic Solar Cells with High Performance of 14.11%", Lingxian Meng, Yamin Zhang, Xiangjian Wan*, Chenxi Li, Xin Zhang, Yanbo Wang, Xin Ke, Zuo Xiao, Liming Ding*, Ruoxi Xia, Hin-Lap Yip, Yong Cao, Yongsheng Chen*,
Science
, 2018, 361, 1094-1098.

"Monolithic 3D Cross-linked Polymeric Graphene Materials and the Likes: Preparation and Their Redox Catalytic Applications",Yanhong Lu, Yanfeng Ma, Tengfei Zhang, Yang Yang, Lei Wei, and Yongsheng Chen ,
Am. Chem. Soc., 2018, 140 (37), pp 11538–11550.

"Ultra-Broadband Wide-Angle Terahertz Absorption Properties of 3D Graphene Foam",Zhiyu Huang, Honghui Chen, Yi Huang,* Zhen Ge, Ying Zhou, Yang Yang, Peishuang Xiao, Jiajie Liang, Tengfei Zhang, Qian Shi, Guanghao Li, and Yongsheng Chen, Funct. Mater. , 2017, 1704363

“Macroscale light propulsion of 3D cross-linked graphene ”, Tengfei Zhang†, Huicong Chang†, Yingpeng Wu†, Peishuang Xiao, Ningbo Yi, Yanhong Lu, Yanfeng Ma, Yi Huang, Kai Zhao, Xiaoqing Yan, Zhibo Liu, Jianguo Tian and Yongsheng Chen*,
Nature Photon., 2015, 9, 471-476
Galvanic Aluminum Bond Pad Corrosion in Copper Wire Bonded Device Assembly – Mechanism and Prevention
Authors: Chyan Oliver , Asokan Muthappan , Thompson Zach , Lambert Alexander , Ross Nick 
Published: February 2020

The explosion of microelectronics use in automobiles has made the microelectronic corrosion control more critical over the past decade. Wire bonded devices form an integral part of the microelectronic systems used in automobiles. With the reliability requirements of automobile microelectronics pushing towards ppb levels of failure, halide induced corrosion issues have to be controlled to achieve such high reliability goals. The corrosion of Aluminum bond pads in slightly acidic chloride solutions (ppm level) has been one of the main modes of wire-bonding failure in wire bonded devices. Earlier researches pointed out the possibility of intermetallic compound formation as the main reason for this corrosion. However, our investigation of the electrochemical nature of the corrosion led to the discovery that bimetallic contact of the aluminum bond pads with copper wires is the main reason for this type of corrosion. Copper and Aluminum being apart in the galvanic series can act as a galvanic corrosion cell under suitable conditions. Furthermore, the presence of halides causes de-passivation of Aluminum oxide layer making the Aluminum bond pad more susceptible to corrosion.
In this report we introduce corrosion screening as a mimicking platform for studying wire-bond device corrosion. For the first time we reported that Hydrogen evolution is the cathodic reaction and is responsible for the explosive nature of this bond pad corrosion. By selective surface treatment of the Cu wires (cathodic part), we were able to prevent the corrosion by blocking the cathodic reaction and thereby stopping the electron flow required for the corrosion cycle to continue. The prevention treatment was then applied to commercial wire-bonded device and excellent corrosion prevention was observed. The corrosion inhibition coating exhibited high thermal stability up to 260
O
C.
We also report a novel testing method for corrosion testing of molded wire-bonded device with internal chloride ion contamination. Electrical continuity and delamination analysis showed that the chosen method of inhibition treatment was able to prevent corrosion even in cases of high chloride contamination and severe delamination. The results of the Pressure Cooker Test showed that the inhibitor coating is suitable for prevention of corrosion in even 100% Relative Humidity environments. Work is now in progress to apply these treatments to Palladium coated Copper wire bonded devices to check corrosion prevention ability of the reported corrosion prevention treatment.
XPS Analysis of the Oxide Films Formed on Non-Charged and Hydrogen-Charged 316L SS in Deaerated High Temperature Water
Authors: Cui Tongming , Ma Jiarong , Zhang Kun , Jia Yibo , Ning Fei , Lu Zhanpeng 
Published: February 2020

Austenitic stainless steel components have been used in pressurized water reactors (PWRs) coolants. These austenitic stainless steels may absorb hydrogen from either the dissociation of dissolved hydrogen in PWR primary water or the corrosion processes at the steel surfaces during the immersion in PWR primary water. It is necessary to investigate the effect of hydrogen in alloys on the oxidation and resultant environmental degradation processes in high temperature water environments. In the present study, the oxide films formed in deaerated PWR primary water at 300℃on a cold worked 316L (316LCW) stainless steel with or without prior hydrogen-charging were characterized. Hydrogen-charging of 316LCW was performed by cathodic charging in sulfuric acid solution containing thiourea at room temperature. Prior to the immersion tests, the Immersion tests were performed in a 2-L Ti-autoclave with solution deaerated by purging N2 gas before heating to test temperature.
The oxide films formed on 316LCW and hydrogen-charged 316L CW (316LCW-H) specimens after exposure to deaerated PWR primary water at 300 oC for168 h were observed. The XPS depth profiles of the oxide films formed on 316LCW and 316LCW-H specimens after exposed to simulated PWR primary water are compared. The thickness of the oxide film was estimated from the half height of oxygen concentration and the sputtering rate (0.1 nm/s), for determining the thickness of the oxide film that was about 180 nm on 316LCW and about 250 nm on 316LCW-H. The oxide films formed on both 316LCW and 316LCW-H were enriched in Fe and Ni in the outer layer, and enriched in Cr in the inner part of the oxide film. The Cr content in the inner oxide layer formed on 316LCW-H specimen was lower than that on 316LCW specimen.

Figure 1
Small Molecule Adsorption on Colloidal Alumina and Zirconia Abrasives Used in Chemical-Mechanical Planarization (CMP) Slurries
Authors: Martinez Keri A. , Stewart Michael R. , Campbell Dean J, , Remsen Edward E. 
Published: February 2020

Small molecule adsorption on CMP slurry abrasive particles has been investigated previously for silica (1) and ceria (2, 3) abrasives using fluorescence correlation spectroscopy (FCS) and attenuated total reflectance – Fourier transform infrared spectroscopy (ATR-FTIR). The need for further characterization of such adsorptive interactions is dictated by the increasing use of abrasive particles in CMP slurries with minimized hydrodynamic diameters (≤ 10 nm) as a means to reduce surface defects created during CMP processes. Incorporation of ever-smaller abrasive particles in CMP slurries will, however, promote the adsorption of chemical additives on a slurry’s abrasive particles due to the increase in the total abrasive particle surface area.
In the present study, FCS and ATR-FTIR are employed in the analysis of small molecule adsorption on colloidal alumina and zirconia abrasive particles. This work is motivated by the widespread commercial use of alumina-based slurries in CMP processes for planarization of deposited copper films on dielectric layers and the proposed use (4) of zirconia abrasives in CMP slurries for metal film removal on dielectric metal oxide materials. The reported FCS studies use fluorescent dyes as probes for adsorption sites on alumina and zirconia colloids dispersed in aqueous solution. Described ATR-FTIR analyses summarize the characterization of molecular interactions driving glycine and picolinic acid adsorption on porous thin films of colloidal alumina and zirconia, respectively. The potential for employing these methods in studies modelling the adsorption of CMP slurry additives on a metal film deposited on a silicon wafer surface is also discussed.

References:

Jacobson, L.M.; Turner, D.K.; Wayman, A.; Rawat, A.; Carver, C.T..; Moinpour, M.; Remsen, E.E. Characterization of Particle Size and Surface Adsorption for SiO2 Abrasives Used in Chemical Mechanical Planarization via Fluorescence Correlation Spectroscopy. ECS J. Solid State Sci. Tech.
2015,
4, P5053-P5057.

Schorr, D.K.; Smith, M.A.; Rawat, A.K.; Carver, C.T.; Mansour, M.; Remsen, E.E.Fluorescence Correlation Spectroscopic Studies of Particle Properties for Colloidal Ceria Abrasives Used in Chemical-Mechanical Planarization. ECS Trans.
2016,
72, 43-51.

Marsh, J.L.; Wayman, A.E.; Smiddy, N.M.; Campbell, D.J.; Parker, J.C.; Bosma, W.B.; Remsen, E.E.Infrared Spectroscopic Analysis of the Adsorption of Pyridine Carboxylic Acids on Colloidal Ceria.Langmuir
2017, 33
, 13224-13233.

“CMP Composition Containing Zirconia Particles and Method of Use”; Lin, Wiechang; Parker, John; Remsen, Elizabeth; PCT Int. Appl. 2012; US 8,778,212 B2; July 15, 2014.
Supercapacitor Prognosis for POWER Electronic Applications
Authors: EL Mejdoubi Asmae , Sabor Jalal , Chaoui Hicham , Gualous Hamid 
Published: February 2020

The lifetime of an energy storage component is the time required to fail. The failure is defined as the lack of ability of a component to fulfill it's specified function. One of its characteristics will be out of the specification. For example the capacitance will be below its specified limit value, or the series resistance will be above its specified value, the component will be leaking, or will be opened.
This paper is about supercapacitor aging and prognosis. At the first, supercapacitor aging according to the temperature and to the voltage is performed. Experimental tests are realized at constant temperature when the supercapacitors are polarized at the maximum voltage. To quantify the supercapacitor aging, the equivalent series resistance and the equivalent capacitance are measured. To lead to the determination of the supercapacitor lifetime, Arrhenius law, that describes the effect of temperature on the velocity of a chemical reaction, is considered.
The second part of this paper presents prognosis model for supercapacitors considering the aging conditions. The proposed model uses the particle filter (PF) to predict the posterior values of the aging indicators, i.e., capacitance and resistance. In order to validate the proposed method, experiments have been carried out under different aging conditions. The PF prognosis results are compared to the experimental ones using the different aging conditions in order to validate the proposed model performance.

Figure 1