- Synthesis and characterization of cross-linkable ruthenium complex dye and its application on dye-sensitized solar cells
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A new crosslinkable light sensitizer, Ru(2,2′-bipyridine- 4,40-bicarboxylic acid)(4,4′-bis(11-dodecenyl)-2,2′-bipyridine)( NCS)2, denoted as Ru-C for titanium oxide nanocrystallinebased solar cells was synthesized with its crosslinking properties invesitigated by Fourier-transform infrared and UV-vis absorption spectroscopies. After crosslinking by itself or copolymerizing with methyacrylic acid, their sensitized solar cells with poly(methylacrylate)-gelled electrolyte system not only attained more than 5% of power conversion efficiency at AM 1.5 illumination (100 mW/cm2), but also gave rise to long storage life. To the best our knowledge, this is the first crosslinkable dye ever applied to the DSSC in the literature.
- Liu, Ken-Yen,Hsu, Chiao-Ling,Chang, Shun-Hsing,Chen, Jian-Ging,Ho, Kuo-Chuan,Lin, King-Fu
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- Magnetic observation of above room-temperature spin transition in vesicular nano-spheres
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Nano-scale materials are acquiring a leading role in the fabrication of new generation devices, especially for the practical application of molecular bi-stability. However, the preparation of purely bi-stable nano-objects without the use of surfactants/polymers remains a challenging task. Here, we present a new approach to prepare spin-crossover (SCO) vesicular nano-spheres with single-external diameters of approximately 100 nm using a CHCl3-H2O mixture. The nano-spheres are based on a series SCO complexes, [Fe(H2Bpz2)2(dialkyl-bipy)] (H2Bpz2 = dihydrobis(1-pyrazolyl)borate, dialkyl-bipy = N4,N4′-dialkyl-(2,2′-bipyridine)-4,4′-dicarbo-xamide, alkyl = propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and cetyl), and are prepared through a self-assembly process that is similar to liposomal assembly, with the dialkyl-bipy moiety acting as the hydrophobic tail and the Fe(H2Bpz2) moiety acting as the hydrophilic head. This study reveals that the alkyl chain length plays a key role in the formation of these nano-spheres and the determination of their spin transition temperatures. The spin transition temperatures for the bulk materials are centered at around 160 K, and show a positive correlation with the alkyl chain length. Meanwhile, for the vesicular nano-spheres in the solid state, their transition temperatures are above room-temperature, and the correlation with the alkyl chain length is negative. These results provide an effective strategy for the design of new metal-organic materials for nano-technological applications.
- Luo, Yang-Hui,Liu, Qing-Ling,Yang, Li-Jing,Sun, Yu,Wang, Jin-Wen,You, Chao-Qun,Sun, Bai-Wang
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- Hexameric supramolecular scaffold orients carbohydrates to sense bacteria
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Carbohydrates are integral to biological signaling networks and cell-cell interactions, yet the detection of discrete carbohydrate-lectin interactions remains difficult since binding is generally weak. A strategy to overcome this problem is to create multivalent sensors, where the avidity rather than the affinity of the interaction is important. Here we describe the development of a series of multivalent sensors that self-assemble via hydrophobic supramolecular interactions. The multivalent sensors are comprised of a fluorescent ruthenium(II) core surrounded by a heptamannosylated β-cyclodextrin scaffold. Two additional series of complexes were synthesized as proof-of-principle for supramolecular self-assembly, the fluorescent core alone and the core plus β-cyclodextrin. Spectroscopic analyses confirmed that the three mannosylated sensors displayed 14, 28, and 42 sugar units, respectively. Each complex adopted original and unique spatial arrangements. The sensors were used to investigate the influence of carbohydrate spatial arrangement and clustering on the mechanistic and qualitative properties of lectin binding. Simple visualization of binding between a fluorescent, multivalent mannose complex and the Escherichia coli strain ORN178 that possesses mannose-specific receptor sites illustrates the potential for these complexes as biosensors.
- Gruenstein, Dan,Maglinao, Maha,Kikkeri, Raghavendra,Collot, Mayeul,Barylyuk, Konstantin,Lepenies, Bernd,Kamena, Faustin,Zenobi, Renato,Seeberger, Peter H.
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- Solid-supported chemiluminescence and electrogenerated chemiluminescence based on a tris(2,2′-bipyridyl)ruthenium(II) derivative
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We report a simple and efficient technique for the covalent immobilisation of a tris(2,2′-bipyridyl)ruthenium(ii) derivative suitable for both chemiluminescence and electrochemiluminescence detection. The Royal Society of Chemistry 2006.
- Greenway,Greenwood,Watts,Wiles
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- Synthesis and recognition behaviour of allosteric hemicarcerands
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Bipyridine bridged bis(resorcinarenes) have been prepared. Upon co-ordinating to a transition metal ion, e.g. Ag+, the respective metal complex forms a hemicarcerand-like structure with the two resorcinarene moieties capable of binding non-polar organic molecules in a co-operative fashion, as shown qualitatively by NMR spectroscopy.
- Lützen, Arne,Ha?, Oliver,Bruhn, Torsten
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- Silver coordination complexes as room-temperature multifunctional materials
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A series of bischelate ionic silver complexes [Ag(L*)2][X] was prepared by complexation of a newly synthesized 2,2′-bipyridine containing chiral alkoxy chains in the 4,4′ positions. The appropriate choice of the construction motifs allows the preparation of new materials in which several functionalities can be introduced.Indeed, when the anion X - is a triflate or a dodecylsulfate group, the right combination of intermolecular interactions promotes the production of liquid crystalline mesophases. Therefore, the presence of coordinating anions, which drives the supramolecular assembly, is essential to generate, at the same time, room-temperature columnar hexagonal mesomorphism, the columnar helical supramolecular structure, and excimeric emission.
- Pucci, Daniela,Barberio, Giovanna,Bellusci, Anna,Crispini, Alessandra,Donnio, Bertrand,Giorgini, Loris,Ghedini, Mauro,La Deda, Massimo,Szerb, Elisabeta Ildyko
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- Protein Surface Mimetics: Understanding How Ruthenium Tris(Bipyridines) Interact with Proteins
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Protein surface mimetics achieve high-affinity binding by exploiting a scaffold to project binding groups over a large area of solvent-exposed protein surface to make multiple cooperative noncovalent interactions. Such recognition is a prerequisite for competitive/orthosteric inhibition of protein–protein interactions (PPIs). This paper describes biophysical and structural studies on ruthenium(II) tris(bipyridine) surface mimetics that recognize cytochrome (cyt) c and inhibit the cyt c/cyt c peroxidase (CCP) PPI. Binding is electrostatically driven, with enhanced affinity achieved through enthalpic contributions thought to arise from the ability of the surface mimetics to make a greater number of noncovalent interactions than CCP with surface-exposed basic residues on cyt c. High-field natural abundance 1H,15N HSQC NMR experiments are consistent with surface mimetics binding to cyt c in similar manner to CCP. This provides a framework for understanding recognition of proteins by supramolecular receptors and informing the design of ligands superior to the protein partners upon which they are inspired.
- Hewitt, Sarah H.,Filby, Maria H.,Hayes, Ed,Kuhn, Lars T.,Kalverda, Arnout P.,Webb, Michael E.,Wilson, Andrew J.
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- Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties
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The reduction of carbon dioxide to chemical fuels such as carbon monoxide is an important challenge in the field of renewable energy conversion. Given the thermodynamic stability of carbon dioxide, it is difficult to efficiently activate this substrate in a selective fashion and the development of new electrocatalysts for CO2 reduction is of prime importance. To this end, we have prepared and studied a new fac-ReI(CO)3 complex supported by a bipyridine ligand containing ancillary BODIPY moieties ([Re(BB2)(CO)3Cl]). Voltammetry experiments revealed that this system displays a rich redox chemistry under N2, as [Re(BB2)(CO) 3Cl] can be reduced by up to four electrons at modest potentials. These redox events have been characterized as the ReI/0 couple, and three ligand based reductions - two of which are localized on the BODIPY units. The ability of the BB2 ligand to serve as a non-innocent redox reservoir is manifest in an enhanced electrocatalysis with CO2 as compared to an unsubstituted Re-bipyridine complex lacking BODIPY units ([Re(bpy)(CO) 3Cl]). The second order rate constant for reduction of CO2 by [Re(BB2)(CO)3Cl] was measured to be k = 3400 M-1 s-1 at an applied potential of -2.0 V versus SCE, which is roughly three times greater than the corresponding unsubstituted Re-bipyridine homologue. Photophysical and photochemical studies were also carried out to determine if [Re(BB2)(CO)3Cl] was a competent platform for CO 2 reduction using visible light. These experiments showed that this complex supports unusual excited state dynamics that precludes efficient CO 2 reduction and are distinct from those that are typically observed for fac-ReI(CO)3 complexes.
- Teesdale, Justin J.,Pistner, Allen J.,Yap, Glenn P.A.,Ma, Ying-Zhong,Lutterman, Daniel A.,Rosenthal, Joel
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- Evaluation of Tris-Bipyridine Chromium Complexes for Flow Battery Applications: Impact of Bipyridine Ligand Structure on Solubility and Electrochemistry
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This report describes the design, synthesis, solubility, and electrochemistry of a series of tris-bipyridine chromium complexes that exhibit up to six reversible redox couples as well as solubilities approaching 1 M in acetonitrile. We have systematically modified both the ligand structure and the oxidation state of these complexes to gain insights into the factors that impact solubility and electrochemistry. The results provide a set of structure-solubility-electrochemistry relationships to guide the future development of electrolytes for nonaqueous flow batteries. In addition, we have identified a promising candidate from the series of chromium complexes for further electrochemical and battery assessment.
- Cabrera, Pablo J.,Yang, Xingyi,Suttil, James A.,Brooner, Rachel E. M.,Thompson, Levi T.,Sanford, Melanie S.
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- Synthesis and characterisation of poly(bipyridine)ruthenium complexes as building blocks for heterosupramolecular arrays
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Poly(bipyridine)ruthenium complexes with carboxylate anchor groups are key components in dye-sensitised solar cells. In this contribution, an improved microwave-assisted synthetic procedure is presented for the important building block [RuCl2(dcmb)2] (dcmb = 4,4′-dimethoxycarbonyl- 2,2′-bipyridine), which results in short reaction times and high purity. The methyl esters are easily deprotected to give free carboxylate functions. In addition, a full structural, spectral and electrochemical characterisation of a series of complexes with the general formula [Ru(dcmb)3-n(tbbpy) n](PF6)2 with n = 0-3 and tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine is presented. The location of the lowest-energy metal-to-ligand charge transfer (MLCT) excited state is investigated by resonance Raman spectroscopy for selected complexes. The results obtained indicate that the nature of the excited state that is populated is dependent on the excitation wavelength. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Schwalbe, Matthias,Schaefer, Bernhard,Goerls, Helmar,Rau, Sven,Tschierlei, Stefanie,Schmitt, Michael,Popp, Juergen,Vaughan, Gavin,Henry, William,Vos, Johannes G.
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- Probing the limits: Ultraslow diffusion and heterogeneous electron transfers in redox polyether hybrid cobalt bipyridine molten salts
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This paper describes microelectrode voltammetry measurements of self-diffusion coefficients and of heterogeneous Co(II/III) electron-transfer rate constants (k°) in undiluted molten salts of three cobalt tris(bipyridine) perchlorate complexes in which the bipyridine ligands are "tailed" with poly(propylene oxide) and poly(ethylene oxide) oligomers. The self-diffusion coefficients are measured with potential step chronoamperometry and range from 10-12 to 10-17 cm2/s, while the quasi-reversible reaction rate constants are measured using cyclic voltammetry and small potential steps and range from 10-7 to 10-12 cm/s. The k° measurements are unusual in that when rate constants become smaller, the reaction remains quasi-reversible, because of concurrently decreasing self-diffusion rates. The measurements are, furthermore, accomplished in the face of uncompensated resistances that range from mega- to gigaohms, which is made possible by the combination of microelectrode properties and small diffusivities. The melt in which self-diffusion and k° values are smallest is at a temperature below its nominal glassing transition and in the regime of molecule-scale diffusion profiles.
- Crooker, Joseph C.,Murray, Royce W.
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- Influence of mono versus bis-electron-donor ancillary ligands in heteroleptic Ru(ii) bipyridyl complexes on electron injection from the first excited singlet and triplet states in dye-sensitized solar cells
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A novel heteroleptic Ru(ii) bipyridyl complex (HD-1-mono) was molecularly designed with a mono-carbazole ancillary ligand, synthesized and characterized for DSCs. The aim was to systematically study the influence of mono (HD-1-mono) versus bis-carbazole ancillary ligand (NCSU-10) on molar absorptivity, light harvesting efficiency (LHE), ground and excited state oxidation potentials, incident-photon-to-current conversion efficiency (IPCE), electron injection from the first excited singlet and triplet states, short-circuit photocurrent density (Jsc), and total solar-to-electric conversion efficiency (η) for DSCs. This study showed that HD-1-mono exhibited slightly lower Voc but greater Jsc compared to NCSU-10. Though HD-1-mono showed lower extinction coefficient than NCSU-10, interestingly, it was found that the decrease in molar extinction coefficient of HD-1-mono is not directly related to the short-circuit photocurrent density (Jsc). For example, HD-1-mono showed a higher Jsc of 21.4 mA cm-2 without the presence of any additives. However, under optimized conditions, HD-1-mono showed a Jsc of 19.76 mA cm-2, Voc of 0.68 V, and (%η) of 9.33 compared to a Jsc of 19.58 mA cm-2, Voc of 0.71 and (%η) of 10.19 for NCSU-10, where N719 achieved a Jsc of 16.85 mA cm-2, Voc of 0.749 V and (%η) of 9.33 under the same experimental device conditions. Impedance results for HD-1-mono showed a shorter recombination time as compared to N719 and NCSU-10, which justify its lower Voc. Femtosecond transient absorption spectroscopy results elucidated that electron injection from the first triplet state is 63% more efficient for HD-1-mono than that of NCSU-10. This journal is the Partner Organisations 2014.
- Cheema, Hammad,Islam, Ashraful,Han, Liyuan,Gautam, Bhoj,Younts, Robert,Gundogdu, Kenan,El-Shafei, Ahmed
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- An efficient preparation of 4,4'-dicarboxy-2,2'-bipyridine
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A convenient and high yield preparation of 4,4'-dicarboxy-2,2'-bipyridine from the oxidation 4,4'-dimethyl-2,2'-bipyridine with potassium dichromate in sulfuric acid is reported.
- Oki,Morgan
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- A Comparative Study on Two RuII Complexes with Thiophene-Based Ancillary Ligands for High-Efficiency Dye-Sensitized Solar Cells
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Heteroleptic polypyridyl Ru complexes MMR-1 and MMR-2 containing 2-(methylthio)thienyl and 2-(4-methoxyphenyl)thienyl units on the antennas of ancillary ligands, respectively, were designed, synthesized, and characterized as sensitizers for dye-sensitized solar cells. The maximum absorption wavelength of MMR-1 is more red-shifted than that of MMR-2, but MMR-2 has a higher molar extinction coefficient, leading to better light harvesting. Under the same device-fabrication conditions, the photovoltaic performances of these sensitizers were evaluated while anchored on mesoporous TiO2 and compared to that of the benchmark N719. Both MMR-1 and MMR-2 exhibited comparable or even higher solar-to-electric conversion efficiencies η with respect to N719 when employed as photosensitizers in DSSCs. Compared to MMR-1, MMR-2 exhibited better overall conversion efficiency, which was attributed to the electron-donating effect of the 4-methoxyphenyl group and the better absorptivity by harvesting higher-energy photons. Complex MMR-2 also showed higher open-circuit voltage VOC than MMR-1, which is likely due to the extension of the antenna of the ancillary ligand by inserting a phenyl group, which leads to less dye aggregation. The photovoltaic performance of MMR-2 was better, with a short-circuit photocurrent density of 16.76 mA cm–2, a VOC of 0.673 V, a fill factor of 73.5 %, and an η value of 8.29 % with the addition of 0.5 m 4-tert-butylpyridine (TBP) compared to 8.18 % for N719.
- Su, Rui,Elmorsy, Mohamed R.,Abed, Mira,Islam, Ashraful,Lord, Meghan,Fadda, Ahmed A.,El-Shafei, Ahmed
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- Induction of mesomorphism through supramolecular association in coordination Pd (II) compounds of dialkyl 2,2′-bipyridine-4,4′-dicarboxylates
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A scries of three 4,4′-disubstituted-2,2′-bipyridines and the corresponding mononuclear cis-dichloro palladium(II) complexes have been synthesized None of the ligands show mesomorphisrn. Upon their complexation to Pd(II) the peculiar structural arrangement characterized by intermolecular associations of the new derivatives induces mesogenic properties, confirming the new and exciting role of the coordination chemistry in metal-mediated formation of liquid crystals.
- Pucci, Daniela,Barberio, Giovanna,Crispini, Alessandra,Ghedini, Mauro,Francescangeli, Oriano
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p. [325]/155-[335]/165
(2003)
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- Synthesis, characterization and photoelectrochemical performance of a tris-heteroleptic ruthenium(II) complex having 4,7-dimethyl-1,10-phenanthroline
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The novel cis-[Ru(Me2-phen)(dcbH2)(NCS)2] complex was prepared using a one-pot route and characterized based on 1H NMR, FTIR, absorption and emission spectra. The properties of this complex were compared with those of cis-[Ru(R2-phen)(dcbH 2)(NCS)2], where R = Ph or H, to establish a relationship between the donor/acceptor character of the R substituent and the observed behavior of these compounds. Computational methods were also employed to gain a comprehensive understanding of this relationship. By using electron-donating/ accepting substituents, it was possible to tune both the ground and excited states of the cis-[Ru(R2-phen)(dcbH2)(NCS)2] complexes. This compound is capable of sensitizing the TiO2 surface and efficiently converting the sunlight into electricity. In comparison to cis-[Ru(Ph2-phen)(dcbH2)(NCS)2] it is observed that the presence of phenyl groups provide higher efficiency. The conversion efficiency was improved in comparison to cis-[Ru(phen)(dcbH2)(NCS) 2]. This increase in efficiency is attributed to an increase in electron density, thus favoring electron transfer to TiO2.
- Carvalho,Liandra-Salvador,Bettanin,Souza,Homem-De-Mello,Polo
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- Synthesis of a Water-Soluble, Soft N-Donor BTzBP Ligand Containing only CHON
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A hydrophilic ligand that contains only C, H, O, and N substituents and uses a 6,6′-bis(1 H -1,2,3-triazol-4-yl)-2,2′-bipyridine (BTzBP) structural core has been synthesized. The effect of adding water-soluble groups onto extractant ligands has been extensively studied to facilitate the efficient partitioning of 4f and transuranic 5f elements for the treatment of spent nuclear fuel. Soft, N-donor ligands exhibit greater binding affinities for the trivalent actinides over the trivalent lanthanides, making BTzBP ligands an ideal candidate in the search for extractants to be used on an industrial scale. To date, hydrophobic BTzBPs have been shown to exhibit physical and chemical properties that might be conducive to nuclear waste processing conditions. However, hydrophilic BTzBPs have yet to be reported. Herein, we show the synthesis of a hydrophilic BTzBP ligand featuring cationic water solubilizing groups attached to the bipyridal rings.
- Albright, Savannah G.,Ali, Bakr,Chapman, Hayley A.,Cheng, Yijie,Cusic, Rachel M.,Friese, Seth J.,Hartlove, Nathan B.,Labb, Samantha A.,Marr, Alissa N.,Masteran, Conner J.,Timmons, Miranda
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supporting information
p. 1384 - 1388
(2020/08/03)
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- Chromium(VI) oxide-mediated oxidation of polyalkyl-polypyridines to polypyridine-polycarboxylic acids with periodic acid
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4,4′-Dicarboxy-2,2′-bipyridine was synthesized quantitatively by chromium(VI) oxide-mediated oxidation of 4,4′-dimethyl-2,2′-bipyridine or 4,4′-diethyl-2,2′-bipyridine with periodic acid as the terminal oxidant in sulfuric acid. 5,5′-Dicarboxy-2,2′-bipyridine and 6,6’-dicarboxy-2,2′-bipyridine were also synthesized by the method from the corresponding dimethyl bipyridines in excellent yields. 4,4′,4″-Tricarboxy-2,2′:6′,2″-terpyridine was obtained in 80% yield from 4,4′,4″-triethyl-2,2′:6′,2″-terpyridine, and 4,4′,4″,4′″-tetracarboxy-2,2′:6′,2″:6″,2′″-quaterpyridine was obtained in 72% yield from 4,4′,4″,4′″-tetraethyl-2,2′:6′,2″:6″,2′″-quaterpyridine by the same procedure.
- Yamazaki, Shigekazu
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supporting information
p. 2210 - 2218
(2019/06/25)
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- Identification of novel lysine demethylase 5-selective inhibitors by inhibitor-based fragment merging strategy
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Histone lysine demethylases (KDMs) have drawn much attention as targets of therapeutic agents. KDM5 proteins, which are Fe(II)/α-ketoglutarate-dependent demethylases, are associated with oncogenesis and drug resistance in cancer cells, and KDM5-selective inhibitors are expected to be anticancer drugs. However, few cell-active KDM5 inhibitors have been reported and there is an obvious need to discover more. In this study, we pursued the identification of highly potent and cell-active KDM5-selective inhibitors. Based on the reported KDM5 inhibitors, we designed several compounds by strategically merging two fragments for competitive inhibition with α-ketoglutarate and for KDM5-selective inhibition. Among them, compounds 10 and 13, which have a 3-cyano pyrazolo[1,5-a]pyrimidin-7-one scaffold, exhibited strong KDM5-inhibitory activity and significant KDM5 selectivity. In cellular assays using human lung cancer cell line A549, 10 and 13 increased the levels of trimethylated lysine 4 on histone H3, which is a specific substrate of KDM5s, and induced growth inhibition of A549 cells. These results should provide a basis for the development of cell-active KDM5 inhibitors to highlight the validity of our inhibitor-based fragment merging strategy.
- Miyake, Yuka,Itoh, Yukihiro,Hatanaka, Atsushi,Suzuma, Yoshinori,Suzuki, Miki,Kodama, Hidehiko,Arai, Yoshinobu,Suzuki, Takayoshi
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p. 1119 - 1129
(2019/02/13)
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- Rational Design of Phosphorescent Iridium(III) Complexes for Selective Glutathione Sensing and Amplified Photodynamic Therapy
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It is a huge challenge to avoid irreversible damage to normal tissues during irradiation in photodynamic therapy (PDT) for cancer. An effective strategy is to develop smart photosensitizers, which exhibit amplified generation of reactive oxygen species (ROS) through triggering specific reaction in the tumor microenvironment. In this work, we designed a class of glutathione (GSH)-activatable photosensitizers (Ir1 and Ir4) based on an effective strategy of GSH-induced nucleophilic substitution reaction. The addition of GSH, induced changes in both phosphorescence intensity and lifetime of photosensitizers with high sensitivity. Importantly, the amount of singlet oxygen generated was increased significantly by GSH-induced activation reaction. Hence, the photosensitizers can selectively distinguish cancer cells from normal cells through luminescence and lifetime imaging, and can amplify PDT effects in cancer cells, owing to the evidently higher level of GSH compared to normal cells. This work presents a novel paradigm for GSH-amplified PDT against cancer cells and provides a new avenue for smart-responsive theranostic systems that can avoid nonspecific damage to normal cells.
- Huang, Tianci,Yu, Qi,Liu, Shujuan,Zhang, Kenneth Yin,Huang, Wei,Zhao, Qiang
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p. 576 - 586
(2018/11/23)
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- Synthesis and characterization of novel heteroleptic Ru(II) bipyridine complexes for dye-sensitized solar cell applications
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Abstract: Four heteroleptic ruthenium(II) complexes, [Ru(L1)(L2)(NCS)2] (where L1 = 4,4′-bis[2-(1,1′-biphenyl)-4-ylethenyl]-2,2′-bipyridine (bpbpy) or 4,4′-bis[2-(3,4-dimethoxyphenyl)ethenyl]-2,2′-bipyridine (dmpbpy); L2 = 4,4′-dicarboxy-2,2′-bipyridine (dcbpy) or 4,4′-bis(E-carboxyvinyl)-2,2′-bipyridine (dcvbpy)), were synthesized from a one-pot reaction of [RuCl2(p-cymene)]2 and L1 followed by the addition of the anchoring ligand, L2. From these new heteroleptic ruthenium(II) complexes containing carboxylic acid-functionalized ligands, the tetrabutylammonium salt forms of the ruthenium(II) complexes, [Ru(L1)(L2)(NCS)2][TBA], were obtained in reasonable yields and applied as dyes in dye-sensitized solar cell (DSSC) devices. Among the DSSCs fabricated with the [Ru(L1)(L2)(NCS)2][TBA] dyes, a DSSC fabricated with the [Ru(bpbpy)(dcbpy)(NCS)2][TBA] dye exhibited the best power conversion efficiency (η) of 4.27%, while the cells fabricated with other dyes had η between 1.94 and 2.68%. Graphic abstract: [Figure not available: see fulltext.].
- Seo, Jinhyung,Jeong, Mingyeong,Na, Seo Yeong,Lee, Eugin,Kim, Yang-Rae,Park, Byoungchoo,Kim, Byeong Hyo
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p. 1445 - 1452
(2019/07/29)
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- Xylose derivatives and process for preparation thereof
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Disclosure of the present invention relates to a method for synthesis of a xylose derivative, which comprises protecting a xylose with a protective group, followed by incorporating to a halogen atom as a leaving group; removing the protective groups and using water-soluble ligands to carry out a Suzuki cross-couplings reaction with a palladium catalyst in a water solution. Ten new xylose derivatives as obtained by the method are also provided.
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Page/Page column 8; 9
(2019/09/01)
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- XYLOSE DERIVATIVES AND PROCESS FOR PREPARATION THEREOF
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Disclosure of the present invention relates to a method for synthesis of a xylose derivative, which comprises protecting a xylose with a protective group, followed by incorporating to a halogen atom as a leaving group removing the protective groups and using water-soluble ligands to carry out a Suzuki cross-couplings reaction with a palladium catalyst in a water solution. Ten new xylose derivatives as obtained by the method are also provided.
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Paragraph 0073-0075
(2020/04/10)
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- Selective Photoinactivation of Methicillin-Resistant Staphylococcus aureus by Highly Positively Charged RuII Complexes
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Ruthenium(II) polypyridyl complexes featuring peripheral quaternary ammonium structures were found to be able to selectively inactivate Gram-positive Staphylococcus aureus (S. aureus), including methicillin-resistant S. aureus (MRSA) upon visible light irradiation, but have low phototoxicity toward 293T cells, L02 cells and lack hemolysis toward rabbit red blood cells (RBC), exhibiting promising potential as a novel type of antimicrobial photodynamic therapy (aPDT) agents.
- Feng, Yang,Sun, Wei-Ze,Wang, Xue-Song,Zhou, Qian-Xiong
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supporting information
p. 13879 - 13884
(2019/11/03)
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- Spectroscopic and 1O2 Sensitization Characteristics of a Series of Isomeric Re(bpy)(CO)3Cl Complexes Bearing Pendant BODIPY Chromophores
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Two new Re(I)bipyridyltricarbonyl chloride complexes, Re(BB3)(CO)3Cl and Re(BB4)(CO)3Cl, featuring BODIPY groups appended to the 5,5′- or 6,6′-positions of the bipyridine ligand, respectively, were synthesized as structurally isomeric compliments to a previously reported 4,4′-substituted homologue, Re(BB2)(CO)3Cl. X-ray crystal structures of the compounds show that the 4,4′-, 5,5′-, and 6,6′-substitution patterns place the BODIPY groups at progressively shorter distances of 9.43, 8.39, and 5.56 ?, respectively, from the complexes' Re centers. The photophysical properties of the isomeric complexes were investigated to ascertain the manner in which the heavy rhenium atom might induce intersystem crossing of the pendant BODIPY moieties positioned at progressively shorter through-space distances. Electronic absorption spectroscopy revealed that the three metal complexes retain the strong visible absorption features characteristic of the bpyBODIPY (BB2-BB4) ligands; however, the fluorescence of the parent borondipyrromethane appended ligands is attenuated by more than an order of magnitude in Re(BB2)(CO)3Cl and Re(BB3)(CO)3Cl and by more than two orders of magnitude in Re(BB4)(CO)3Cl. Furthermore, phosphorescence from Re(BB4)(CO)3Cl is observed under a nitrogen atmosphere, consistent with highly efficient ISC to the triplet-excited state. Singlet oxygen sensitization studies confirm that all three complexes produce singlet oxygen with quantum yields that increase as the distance of the BODIPY groups to the heavy rhenium center is decreased. The trends observed across the series of rhenium complexes with respect to emission and 1O2 sensitization properties can be rationalized in terms of the varied distal separation between the metal center and BODIPY groups in each system.
- Potocny, Andrea M.,Teesdale, Justin J.,Marangoz, Alize,Yap, Glenn P. A.,Rosenthal, Joel
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supporting information
p. 5042 - 5050
(2019/04/25)
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- Compound based on inhibiting histone demethylase as well as preparation method thereof and application in resisting gastric carcinoma
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The invention provides a compound WXSA-082B based on inhibiting histone demethylase, further provides a preparation method thereof. Tests shown that the compound can enable H3K4me3 protein level in human gastric carcinoma cell BGC-823 to increase obviously, has obvious RBP2 enzyme activity inhibiting effect, and can reduce the transfer ability of the human gastric carcinoma cell BGC-823. The compound provided by the invention can be applied to preparation of anti-gastric carcinoma drugs serving as a gastric carcinoma inhibitor. The structure of the compound is as follows: (the structure is shown in the description).
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Paragraph 0024; 0025
(2019/03/28)
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- Synthesis and Characterization of Heteroleptic Ru(II) Complexes Based on 4,4′-Bis((E)-styryl)-2,2′-bipyridine as Ancillary Ligand and Application for Dye-Sensitized Solar Cells
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Heteroleptic Ru(II) complexes were designed based on 4,4′-bis((E)-styryl)-2,2′-bipyridine (bsbpy) as an ancillary ligand for dye-sensitized solar cells (DSSCs), and those Ru(II) sensitizers, [Ru(L)(bsbpy)(NCS)2][TBA] (TBA; tetrabutylammonium), were synthesized according to a typical one-pot reaction of [RuCl2(p-cymene)]2 with the corresponding anchoring ligands (where L?=?4,4′-dicarboxy-2,2′-bipyridine (dcbpy), 4,4′-bis((E)-carboxyvinyl)-2,2′-bipyridine (dcvbpy), 4,7-dicarboxy-1,10-phenanthroline (dcphen), or 4,7-bis((E)-carboxyvinyl)-1,10-phenanthroline (dcvphen)). The new Ru(II) dyes, [Ru(L)(bsbpy)(NCS)2][TBA] that incorporated vinyl spacer(s) into ancillary and/or anchoring ligand displayed red-shifted bands over the overall UV/VIS region relative to the absorption spectra of N719. A combination of bsbpy ancillary and dcphen anchoring ligand showed the best result for the overall power conversion efficiency (η); i.e., a DSSC fabricated with [Ru(dcphen)(bsbpy)(NCS)2][TBA] exhibited a power conversion efficiency (η) of 2.98% (compare to N719, 4.82%).
- Lee, Jihoon,Seo, Jinhyung,Choi, Yong Rack,Oh, Hyunju,Huh, Jun Nyeong,Park, Byoungchoo,Tak, Jungae,Kim, Byeong Hyo
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- New amide based iridium(III) complexes: Synthesis, characterization, photoluminescence and DFT/TD-DFT studies
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New iridium(iii) complexes with 2-(3-fluorophenyl)-4-methylpyridine as cyclometalated ligands and 2,2′-bipyridine-4,4′-dicarboxamide derivatives as ancillary ligands were synthesized and characterized by FTIR, NMR, MS, UV/Visible, and fluorescence spectroscopies and cyclic voltammetry. The effects of different solvents and substituents on the photophysical properties of the complexes have been investigated. The complexes show tunable photoluminescence wavelengths depending on solvent polarity in the 548 nm to 610 nm range where the emission colour can change from green to orange-red. The complexes exhibit high photoluminescence quantum yields between 0.41 and 0.75, which may be attributed to the change in the transition dipole moment originating from the amide group upon electronic excitation. The calculated HOMO and LUMO energy levels of complexes 1-7 are in the -5.51 to -5.60 eV and -3.37 to -3.40 eV ranges, respectively. The ground and excited state properties of 1 have been fully investigated by means DFT and TD-DFT methods respectively. The general trends of observed data have been successfully represented and quantified by computational data.
- Sahin, Cigdem,Goren, Aysen,Demir, Serkan,Cavus, Muhammet Serdar
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p. 2979 - 2988
(2018/02/19)
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- Tandem one-pot CO2 reduction by PMHS and silyloxycarbonylation of aryl/vinyl halides to access carboxylic acids
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The present study discloses the synthesis of aryl/vinyl carboxylic acids from Csp2-bound halides (Cl, Br, I) in a carbonylative path by using silyl formate (from CO2 and hydrosilane) as an instant CO-surrogate. Hydrosilane provides hydride for reduction and its oxidation product silanol serves as a coupling partner. Mono-, di-, and tri-carboxylic acids were obtained from the corresponding aryl/vinyl halides.
- Paridala, Kumaraswamy,Lu, Sheng-Mei,Wang, Meng-Meng,Li, Can
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supporting information
p. 11574 - 11577
(2018/10/31)
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- Ionic type iridium complex with double phosphorescence emission properties as well as preparation method and application of ionic type iridium complex
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The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to an ionic type iridium complex with double phosphorescence emission properties as well as a preparation method and an application of the ionic type iridium complex. The complex comprises a metal center and cyclometalated ligands. The preparation method comprises steps as follows: dichloro bridge is prepared from a phenylpyridine derivative and iridium(III) chloride trihydrate through a coordination reaction, and the ionic type iridium complex with the double phosphorescence emission properties is prepared from dichloro bridge and a dipyridyl derivative or sodium carbonate through coordination reaction. The ionic type iridium complex with the double phosphorescence emission properties can be applied to the fields of biological detection and biological imaging for hypoxic oxygen-enriched conditions; a diagnosis and treatment integrated multifunctional probe based on the ionic type iridium complex with the double phosphorescence emission properties has great potential in further biomedicine application.
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Paragraph 0051-0054
(2018/01/11)
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- A 2, 2° - bipyridyl - 4, 4° - phthalic acid preparation method
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The invention discloses a preparation method of 2'-bipyridine-4,4'-dicarboxylic acid, belonging to the technical field of synthesis of sensitization fuel and medicinal intermediates. The point of the technical scheme adopted in the invention is as follows: 4,4'-dimethyl-2,2'-bipyridine is dissolved in a mixed system of water and nitric acid, and the 2'-bipyridine-4,4'-dicarboxylic acid is prepared through the oxidation of potassium permanganate. The method disclosed by the invention is easy to operate, the reaction conditions are mild, the reaction time is relatively short, and the yield of the obtained product is relatively high; and moreover, the after-treatment of the reaction is simple, the product is easily crystallized and separated from the system and is convenient to separate to obtain the target compound, and the method is suitable for large-scale production.
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Paragraph 0029-0031
(2017/10/06)
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- Directly Coupled Versus Spectator Linkers on Diimine PtII Acetylides—Change the Structure, Keep the Function?
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Modification of light-harvesting units with anchoring groups for surface attachment often compromises light-harnessing properties. Herein, a series of [donor–acceptor–anchor] platinum(II) diimine (bis-)acetylides was developed in order to systematically compare the effect of conjugated versus electronically decoupled modes of attachment of protected anchoring groups on the photophysical properties of light-harvesting units. The first examples of “decoupled” phosphonate diimine PtII complexes are reported, and their properties are compared and contrasted to those of carboxylate analogues studied by a diversity of methods. Ultrafast time-resolved IR and transient absorption spectroscopy revealed that all complexes have a charge-transfer (CT) lowest excited state with lifetimes between 2 and 14 ns. Vibrational signatures and dynamics of CT states were identified; the assignment of electronic states and their vibrational origin was aided by TDDFT calculations. Ultrafast energy redistribution accompanied by structural changes was directly captured in the CT states. A significant difference between the structures of the electronic ground and CT excited states, as well as differences in the structural reorganisation in the complexes bearing directly attached or electronically decoupled anchoring groups, was discovered. This work demonstrates that decoupling of the anchoring group from the light-harvesting core by a saturated spacer is an easy approach to combine surface attachment with high reduction potential and ten times longer lifetime of the CT excited state of the light-absorbing unit, and retain electron-transfer photoreactivity essential for light-harvesting applications.
- Archer, Stuart A.,Keane, Theo,Delor, Milan,Bevon, Elizabeth,Auty, Alexander J.,Chekulaev, Dimitri,Sazanovich, Igor V.,Towrie, Michael,Meijer, Anthony J. H. M.,Weinstein, Julia A.
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p. 18239 - 18251
(2017/12/07)
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- Effect of the CF3 Substituents on the Charge-Transfer Kinetics of High-Efficiency Cyclometalated Ruthenium Sensitizers
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Six thiocyanate-free complexes, DUY1-DUY6, were synthesized, and their application in a dye-sensitized solar cell was studied to explore the effect of the CF3 substituent positioned in the ancillary ligand and the structure of the anchoring ligand on the physicochemical properties, charge-transfer kinetics, and photovoltaic properties of ruthenium sensitizers. When the electron-withdrawing groups were installed on the cyclometalating ligands and their π conjugation of the ancillary ligand was extended, the frontier orbital energy levels of the ruthenium complex appeared to be sufficient for effective electron injection and dye regeneration, at the same time having high light-harvesting ability. Two electron-withdrawing CF3 groups meta to the cyclometalated position reduce the electron density at the metal center less seriously than o-CF3 and p-CF3 groups. The sensitizers containing a m-CF3 group also reveal a more favorable distribution of β lowest unoccupied spin orbital for interaction between the oxidized dyes and the iodide ion, which promotes dye regeneration. The absorption profiles of DUY1-DUY4 adsorbed a TiO2 film extended to longer wavelength compared to those in an N,N-dimethylformamide solution, especially DUY1 and DUY2 dyes, which have λmax red shifts of up to 30 nm. The DUY2-dyed cell exhibited the highest efficiency of 9.03%, while the power conversion efficiencies of DUY1-, DUY3-, DUY4-, and N719-based devices were 7.40%, 7.01%, 8.92%, and 8.63%, respectively. DUY5 and DUY6 (the side products of DUY3 and DUY4) without anchoring groups have very weak physical adsorption on a TiO2 anode. The corresponding cells exhibit very low efficiency (0.1%), although both dyes have high light-harvesting ability and proper frontier orbital energy levels.
- Nguyen, The-Duy,Lin, Chun-Han,Wu, Chun-Guey
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supporting information
p. 252 - 260
(2017/01/13)
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- Thiocyanate-free ruthenium(II) sensitizers with a bi-imidazole ligand in dye-sensitized solar cells (DSSCs)
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In this study, tris-heteroleptic Ru(ii) sensitizers denoted as SD-15 and SD-16 with a 4,4′,5,5′-tetramethyl-1H,1′H-2,2′-bis-imidazole moiety as the ancillary ligand were designed, synthesized and characterized using FTIR-ATR, 1H-NMR and UV-vis spectrophotometry. Structural modulations resulted in a red shift in the low-energy metal-to-ligand charge transfer (MLCT) absorption peak. The novel bis-imidazole based Ru(ii) sensitizer was adsorbed on a TiO2 surface via -COOH anchoring groups. The band gap, and the ground and excited state oxidation potentials were measured. The photovoltaic performance of the as-fabricated solar cells was measured and showed that the presence of bis-imidazole provided more negative free energy for dye regeneration (-ΔGregeneration) and less driving force for electron injection (-ΔGinjection) into the conduction band edge of TiO2. Therefore, the use of SD-15 and SD-16 resulted in lower JSC values of 10.20 and 3.52 mA cm-2, respectively, than N719. The open-circuit photovoltage (VOC) of SD-15 and SD-16 was 0.58 and 0.52 V, respectively, less than N719 under the same experimental conditions due to the decreased eTiO2 lifetime of 0.71 ms compared to 8.8 ms of N719 for the injected electrons that was calculated using impedance measurements. Our efforts in this research program led to the development of more stable Ru(ii) complexes compared to N719 NCS-based complexes; however, the conversion efficiency was lower. Hence, the fine-tuning of bi-imidazole is needed to identify more efficient NCS-free Ru(ii) sensitizers for higher efficiency DSSCs.
- Ashraf, Saba,Akhtar, Javeed,Siddiqi, Humaira M.,El-Shafei, Ahmed
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supporting information
p. 6272 - 6277
(2017/07/17)
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- Threading of various 'U' shaped bidentate axles into a heteroditopic macrocyclic wheel: Via NiII/CuII templation
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The threading of 'U' shaped bent axles having diverse functionalities (Axle1-Axle10) is investigated by using a heteroditopic amido-amine macrocyclic (MC) wheel via NiII or CuII metal ion templation. These bent shaped axles are the derivatives of 4,4′-substituted 2,2′-bipyridine, which are composed of various terminal groups like alkene, alkyne, bromide, hydroxyl and azide. Such metallo [2]pseudorotaxanes are well characterised by ESI-MS, EPR and FT-IR spectroscopic studies, UV-Vis absorption studies, elemental analysis and single-crystal X-ray diffraction studies wherever possible. Experimental evidence supports 1:1:1 ternary complexation between MC, the metal ion and axle. The single crystal X-ray structures of three CuII templated ternary complexes (PR1′, PR3′ and PR7′) show the penta-coordination arrangement around the templating metal ion. Interestingly, judicious selection of chemical functionalities in the complementary wheel and axle components enables to show the existence of various covalent and non-covalent interactions.
- Nandi, Mandira,Santra, Saikat,Akhuli, Bidyut,Ghosh, Pradyut
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p. 7421 - 7433
(2017/07/10)
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- Covalent hybrids based on Re(i) tricarbonyl complexes and polypyridine-functionalized polyoxometalate: Synthesis, characterization and electronic properties
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A series of [Re(CO)3Br(N^N)] (N^N = substituted 2,2′-bipyridine ligand) complexes based on polypyridine-functionalized Dawson polyoxometalate (1-3) has been synthesized. The new hybrids (4-6) were characterized by various analytical techniques, including absorption, vibrational and luminescence spectroscopies as well as electrochemistry. Both units, the polyoxometalate and the transition metal complex, retain their intrinsic properties. Their combination in the newly prepared hybrids results in improved photosensitization in the high-energy visible region. However, a complete quenching of the emission for the [Re(CO)3Br(N^N)] complexes is observed due to formation of a charge separated state, Re(ii)-POM-, as shown by quenching experiments as well as theoretical modelling via DFT.
- Auvray, Thomas,Santoni, Marie-Pierre,Hasenknopf, Bernold,Hanan, Garry S.
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supporting information
p. 10029 - 10036
(2017/08/10)
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- A kind of induction of cell expansion die of the iridium complex and its preparation method and anti-tumor application (by machine translation)
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The invention discloses a induced cell expansion die of the ring metal metallation complex and its preparation method and anti-tumor application. The ring metal metallation complex shown in the following formula: The invention of the ring metal metallation complex to the human body a plurality of cancer cells including its strain of drug resistant strain of drug with very strong growth inhibiting ability, and its mechanism of action is based on the mitochondrial targeting rather than traditional nuclear targeting, inducing cell expansion die instead of the new mechanism of apoptosis, can overcome the drug resistance of tumor cells to tumor treatment of the defect, in the development of efficient anti-cancer medicine has very good application prospect. (by machine translation)
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Paragraph 0084; 0087-0088
(2017/08/31)
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- A water-soluble and retrievable ruthenium-based probe for colorimetric recognition of Hg(II) and Cys
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A new ruthenium-based complex 1 [(bis(4,4′-dimethylphosphonic-2,2′-bipyridine) dithiocyanato ruthenium (II))] was developed as a colorimetric probe for the detection of Hg(II) and Cys (Cysteine). The obtained compound 1 can give interconversional color changes upon the alternating addition of Hg(II) and Cys in 100% aqueous solution. The specific coordination between NCS groups with Hg(II) can lead to the formation of 1-Hg2 + complex, which can induce a remarkable spectral changes of probe 1. Afterwards the formed 1-Hg2 + complex can act as effective colorimetric sensor for Cys. Owing to the stronger binding affinity of sulfhydryl group to Hg2 +, Cys can extract Hg2 + from 1-Hg2 + complex resulting in the release of 1 and the revival of absorption profile of the probe 1. By introducing the hydrophilic phosphonic acid groups, the proposed probe exhibited excellent water solubility. The limits of detection (LODs) of the assay for Hg2 + and Cys are calculated to be 15 nM and 200 nM, respectively.
- Cui, Yali,Hao, Yuanqiang,Zhang, Yintang,Liu, Baoxia,Zhu, Xu,Qu, Peng,Li, Deliang,Xu, Maotian
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supporting information
p. 150 - 154
(2016/05/09)
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- A high efficiency ruthenium(II) tris-heteroleptic dye containing 4,7-dicarbazole-1,10-phenanthroline for nanocrystalline solar cells
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The tris-heteroleptic polypyridyl ruthenium(ii) dye, cis-[Ru(cbz2-phen)(dcbH2)(NCS)2], cbz2-phen = 4,7-dicarbazole-1,10-phenanthroline and dcbH2 = 4,4′-dicarboxylic acid 2,2′-bipyridine, was designed, synthesized, purified via liquid chromatography and characterized using 1H NMR, FTIR, cyclic voltammetry, absorption and emission spectroscopy. The compound exhibits broad and intense MLCT bands that overlap the visible spectrum and it is capable of sensitizing TiO2 films. The energy levels of cis-[Ru(cbz2-phen)(dcbH2)(NCS)2] are adequate for its use in DSSCs. The solar cells prepared using this dye achieved a performance that surpasses N3 dye under the same conditions. The introduction of the extended π-conjugated carbazole substituent at the 4 and 7 positions of 1,10-phenanthroline increases the IPCE and the overall solar cell efficiency. The high performance is ascribed to the HOMO stabilization and to the increase in electron delocalization of the triplet excited state, which favors the electron injection via singlet and triplet pathways.
- Müller, Andressa V.,Ramos, Luiz D.,Frin, Karina P. M.,De Oliveira, Kleber T.,Polo, André S.
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p. 46487 - 46494
(2016/06/06)
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- Post-synthetic modifications of cadmium-based knots and links
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Three topologically non-trivial cadmium(ii)-based complexes - Cd-[2]C, Cd-TK and Cd-SL - were simultaneously self-assembled in a dynamic library, individually isolated and fully characterized using solid-state, gas-phase and solution-phase techniques. Post-synthetic modifications, including reduction and transmetalation, were subsequently achieved. Imine bond reduction followed by demetallation led to the isolation of the corresponding organic molecules [2]C, TK and SL. Transmetalation of Cd-TK and Cd-SL with the zinc(ii) cation resulted in isolation of the corresponding zinc(ii)-containing complexes Zn-TK and Zn-SL.
- Prakasam, Thirumurugan,Bilbeisi, Rana A.,Lusi, Matteo,Olsen, John-Carl,Platas-Iglesias, Carlos,Trabolsi, Ali
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supporting information
p. 7398 - 7401
(2016/06/14)
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- Copper oxide surfaces modified by alkylphosphonic acids with terminal pyridyl-based ligands as a platform for supported catalysis
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Self-assembled monolayer (SAM) films of phosphonates have been successfully formed via reaction of 11-hydroxyundecylphosphonic acid or 4,4′-di(methylenephosphonic acid)-2,2′-bipyridine with the oxide layer of copper via the Tethering by Aggregation and Growth (TBAG) deposition method. The hydroxyl-terminated SAM was further modified with isonicotinic acid or 4,4′-dicarboxy-2,2′-bipyridine through a Steglich esterification reaction. These three surfaces derivatized with pyridyl-based ligands are potential platforms for supported catalysis. As a proof of concept, [Ru(CO)3Cl2]2 was bound to the surfaces through the pyridyl-based ligands to yield tethered analogs of the known carbon dioxide reduction catalyst, [Ru(bpy)(CO)2Cl2]. Surface modification reactions were confirmed through specular reflectance infrared (IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Characteristic core binding energies were observed in the XPS analyses for phosphorus (P 2p), nitrogen (N 1s), and ruthenium (Ru 3p and Ru 3d), verifying the presence of the various surface functionalizations. IR and XPS data indicate that the phosphonate binding to the copper surface is tridentate in nature.
- Andrews, Brooke,Almahdali, Sarah,James, Karmel,Ly, Sandrine,Crowder, Katherine N.
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p. 360 - 369
(2016/07/06)
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- Metal-based tris-bipyridyl complexes and uses thereof in electrochromic applications
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The present invention relates to metal-based tris-bipyridyl complexes, e.g., iron-based tris-bipyridyl complexes, and their use in fabrication of surface confined assemblies for electrochromic applications.
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Paragraph 0127; 0159
(2016/10/09)
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- Pyridinium-based ionic phosphorescent iridium complex probe and preparation method and biotechnological application thereof
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The invention relates to a pyridinium-based ionic phosphorescent iridium complex probe and a preparation method and biotechnological application thereof, in particular to phosphorescent iridium complex for detecting and reducing glutathione, cysteine, hydrogen sulfide and other sulfydryl containing reductive substances and application of the phosphorescent iridium complex in detecting the redox state in cells, and belongs to the technical field of organic photoelectric functional materials. The complex material is prepared from cyclometalated ligand, a metal center (iridium) and pyridinium group modified auxiliary ligand, and the structure of the complex is shown as the following formula. The complex has wide application prospects on the technical aspects of detecting the redox state in the cells, phosphorescence lifetime imaging and time resolution. The formula can be seen in the specification.
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Paragraph 0023; 0025; 0027
(2017/11/07)
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- Isomer Dependence of Efficiency and Charge Recombination in Dye-Sensitized Solar Cells Using Ru Complex Dyes Bearing Halogen Substituents
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We have synthesised Ru(H2-dcbpy)(N,N′-Y2-bpy)(NCS)2 dyes (where N = 4, 5; Y = F, Cl, Br; N is the position on the bipyridyl ring where the halogen substituent is located) for dye-sensitised solar cells. We show that careful consideration of the position of the substituent, in conjunction with the nature of the substituents, on a bpy ring is important to optimize the solar cells performance. Changing the position (from 4,4′ to 5,5′) along with the nature of the halogen (F, Cl, or Br) substituents were observed to cause changes in the electronic and spectroscopic properties of the dyes as well as influence the recombination rates at the TiO2-dyes-I-/I3- interface affecting the performance of the dyes in DSSCs. Changing the position (from 4,4′ to 5,5′) along with the nature of the halogen (F, Cl, or Br) substituents affects the electronic and spectroscopic properties of the Ru(H2-dcbpy)(N,N′-Y2-bpy)(NCS)2 dyes as well as the recombination rates at the TiO2-dyes-I-/I3- interface hence affecting the performance of the dyes in DSSCs.
- Chadwick, Nina,Kumar, D. Kishore,Ivaturi, Aruna,Grew, Benjamin A.,Upadhyaya, Hari M.,Yellowlees, Lesley J.,Robertson, Neil
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supporting information
p. 4878 - 4884
(2015/11/02)
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- Dynamic stereoisomerization in inherently chiral bimetallic [2]catenanes
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Stereoisomerization and the unprecedented phenomenon of metal translocation in the absence of redox processes were probed in two inherently chiral bimetallic [2]catenanes by using a combination of variableerature 1H NMR and CD spectroscopies, X-ray crystallography, and DFT calculations.
- Prakasam, Thirumurugan,Lusi, Matteo,Nauha, Elisa,Olsen, John-Carl,Sy, Mohamadou,Platas-Iglesias, Carlos,Charbonnière, Lo?c J.,Trabolsi, Ali
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supporting information
p. 5840 - 5843
(2015/03/31)
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- Ruthenium bipyridyl tethered porous organosilica: A versatile, durable and reusable heterogeneous photocatalyst
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A versatile heterogeneous photocatalysis protocol was developed by using ruthenium bipyridyl tethered porous organosilica (Ru-POS). The versatility of the Ru-POS catalyst in organo-photocatalysis was explored by (i) oxidative aromatization of Hantzsch ester, (ii) reductive dehalogenation of alkyl halides, and (iii) functional group interconversion (FGI) of alcohols to alkyl halides. This journal is
- Jana, Avijit,Mondal, John,Borah, Parijat,Mondal, Sujan,Bhaumik, Asim,Zhao, Yanli
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supporting information
p. 10746 - 10749
(2015/06/30)
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- Synthesis, characterization, and luminescent property of amide functionalized ruthenium(II) complexes
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Amide functionalized bipyridine ligands and their ruthenium(II) complexes of the type [Ru(bipyridine)2(L)](PF6)2 were synthesized and characterized by UV/Visible, emission, FTIR, 1H NMR spectroscopies and elemental analysis. Thermal properties of the ruthenium(II) polypyridyl complexes have been investigated using thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques. These complexes show remarkable thermal stability at high temperatures under nitrogen atmosphere. The ruthenium(II) complexes show increasing fluorescence intensity in the presence of the amide groups. The increase of the emission intensity and quantum yield of the molecules may be attributed to the change of dipole moment of the amide group on electronic excitation. The effects of substituent (-CH3, -OCH3, -COOC2H5, -COOH) on photophysical properties of molecules were correlated with the Hammett Substituent Constants. The molecules exhibit linear correlation for absorption and emission maxima.
- Sahin, Cigdem
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p. 250 - 263
(2015/03/30)
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- Helical Channel Mesoporous Materials with Embedded Magnetic Iron Nanoparticles: Chiral Recognition and Implications in Asymmetric Olefin Epoxidation
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In this work a mesoporous nanocomposite material comprising helical chiral channels and with embedded magnetic iron oxide nanoparticles in its Si-based MCM-41 type framework was synthesized. Afterwards, a bipyridine derivative was grafted to the inner surface used as ligand to coordinate a molybdenum(II) precursor complex. The Mo loading was found to be 2.42 wt% Mo, corresponding to 0.26 mmolMo g-1. The successful preparation of this helical mesoporous material was evidenced by an extensive characterization process using powder XRD, SEM/TEM analysis, FT-IR and Raman spectroscopies, TGA analysis and also by SQUID measurements. Selective adsorption of enantiopure D- and L-phenylalanine shows that the material has a preference for the D- over the L- enantiomer. This provides evidence that the channels are chiral (although the particles are not) and that it is useful for chiral recognition applications. It also sets the explanation to the good results achieved in the selective epoxidation of olefins. The resulting material was tested as catalytic precursor in the epoxidation of cis-cyclooctene, styrene, R-(+)-limonene and trans-hex-2-en-1-ol, using tert-butyl hydroperoxide (tbhp) as oxygen source. The catalytic studies show that the synthesized material yields selectively the desired epoxides of the tested substrates with very good results, especially at higher temperatures and using toluene as solvent. The major achievement of the catalyst was an outstanding stereocontrol of the reaction products imposed by the confined space of the helical chiral channels. Therefore these materials offer an important contribution to asymmetric catalysis and to fields where chiral recognition is a relevant concept.
- Fernandes, Cristina I.,Stenning, Gavin B. G.,Taylor, James D.,Nunes, Carla D.,D. Vaz, Pedro
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p. 3127 - 3140
(2015/11/03)
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- Synthesis and characterization of an immobilizable photochemical molecular device for H2-generation
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With [RuII(bpyMeP)2tpphzPtCl2]2+ (4) a molecular photocatalyst has been synthesized for visible-light-driven H2-evolution. It contains the ligand bpyMeP (4,4′-bis(diethyl-(methylene)-phosphonate)-2,2′-bipyridine) with phosphate ester groups as precursors for the highly potent phosphonate anchoring groups, which can be utilized for immobilization of the catalyst on metal-oxide semiconductor surfaces. The synthesis was optimized with regard to high yields, bpyMeP was fully characterized and a solid-state structure could be obtained. Photophysical studies showed that the photophysical properties and the localization of the excited states are not altered compared to similar Ru-complexes without anchoring group precursors. (4) was even more active in homogenous catalysis experiments than [RuII(tbbpy)2tpphzPtCl2]2+ (6) with tbbpy (4,4′-bis(tbutyl)-2,2′-bipyridine) as peripheral ligands. After hydrolysis (4) was successfully immobilized on NiO, suggesting that an application in photoelectrosynthesis cells is feasible. This journal is
- Braumüller, Markus,Schulz, Martin,Sorsche, Dieter,Pfeffer, Michael,Schaub, Markus,Popp, Jürgen,Park, Byung-Wook,Hagfeldt, Anders,Dietzek, Benjamin,Rau, Sven
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supporting information
p. 5577 - 5586
(2015/03/30)
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- DYE SENSITIZED SOLAR CELL COMPRISING NOVEL BIPYRIDINE RUTHEMIUM BASED DYE
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The present invention provides a dye-sensitized solar cell comprising: a first electrode; an optical absorbing layer formed on one surface of the first electrode, and including at least one of bipyridine ruthenium-based compounds represented by the chemical formula (1), chemical formula (2), and chemical formula (3) as a bipyridine ruthenium-based dye; a second electrode disposed to face the first electrode having the optical absorbing layer formed thereon; and an electrolyte layer formed between the first electrode and the second electrode.COPYRIGHT KIPO 2016
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- Synthesis and electron-transfer processes in a new family of ligands for coupled Ru-Mn2 complexes
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A series of [Ru(bpy)3]2+-type (bpy=2,2 ′-bipyridine) photosensitisers have been coupled to a ligand for Mn, which is expected to give a dinuclear complex that is active as a water oxidation catalyst. Unexpectedly, photophysical studies showed that the assemblies had very short lived excited states and that the decay patterns were complex and strongly dependent on pH. One dyad was prepared that was capable of catalysing chemical water oxidation by using [Ru(bpy)3]3+ as an oxidant. However, photochemical water oxidation in the presence of an external electron acceptor failed, presumably because the short excited-state lifetime precluded initial electron transfer to the added acceptor. The photophysical behaviour could be explained by the presence of an intricate excited-state manifold, as also suggested by time-dependent DFT calculations.
- Karlsson, Erik A.,Lee, Bao-Lin,Liao, Rong-Zhen,Akermark, Torbjoern,Kaerkaes, Markus D.,Becerril, Valeria Saavedra,Siegbahn, Per E. M.,Zou, Xiaodong,Abrahamsson, Maria,Akermark, Bjoern
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p. 936 - 950
(2014/08/05)
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- Synthesis of bifunctional Ru complexes with 1,2-dithiolane and carboxylate-substituted ligands
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Abstract An N3-type, Ru heteroleptic complex, AK1, having one bipyridyl ligand modified with COOH groups for tethering to TiO2 and a second bipyridyl ligand modified with two lipoic acid units for binding to platinum, was synthesized. The photophysical and spectroelectrochemical properties were studied in solution, on TiO2, in a dye-sensitized solar cell and on a Pt wire electrode. The results showed that AK1 can produce a photocurrent on TiO2. Furthermore, AK1 binds to Pt via the lipoic acid ligand but not via the carboxylic acid group, and can be electrochemically addressed by the Pt via the lipoic acid linkage.
- Kopecky, Andrew,Liu, Guangliang,Agushi, Ardian,Agrios, Alexander G.,Galoppini, Elena
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p. 6271 - 6275
(2015/05/27)
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- Highly enantioselective olefin epoxidation controlled by helical confined environments
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Helical mesoporous materials of the MCM-41 type are important materials that can be prepared by onepot synthesis procedures with a co-surfactant. A control of the characteristics at a local level is of the most important in the view of the applications of such materials. However, there are not many studies relating such features with synthetic approaches. In this work, we prepared both helical and regular channel materials from Si-based MCM-41 type. Afterward, a bpy derivative was used as ligand to coordinate MoII/VI. The complexes and the new materials were tested as the catalytic precursors in the epoxidation of cis-cyclooctene, styrene, 1-octene, R-(+)-limonene and trans-hex-2-en-1-ol, using tert-butylhydroperoxide (TBHP) as oxidant. Although almost all the catalysts were 100% selective toward the epoxide, the conversions were in general good. The major achievement of these catalysts is an outstanding stereocontrol of the reaction products. In addition, these catalysts were found to be very effective under several circumstances. This is certainly an important contribution for such concept and may render such materials further applications where chiral recognition is important.
- Fernandes, Cristina I.,Saraiva, Marta S.,Nunes, Teresa G.,Vaz, Pedro D.,Nunes, Carla D.
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- Tuning the photophysical and electrochemical properties of iridium(III) 2-aryl-1-phenylbenzimidazole complexes
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A series of heteroleptic bis-cyclometalated iridium(III) complexes, [Ir(cpbi)2(H2dcbpy)][PF6] (1), [Ir(pbi) 2(H2dcbpy)][PF6] (2), and [Ir(mpbi) 2(H2dcbpy)][PF6] (3), where pbi = 1,2-diphenylbenzimidazole, cpbi = 2-(4-chlorophenyl)-1-phenylbenzimidazole, mpbi = 2-(3,4-dimethoxyphenyl)-1-phenylbenzimidazole, and H2dcbpy = 2,2′-bipyridine-4,4′-dicarboxylic acid has been synthesized and characterized by elemental analysis, 1H, 31P NMR, and high resolution mass-spectra. Molecular structure of complex 3 has been determined from single-crystal X-ray analysis. The complexes exhibit absorption up to 550 nm with molar absorptivities of 2500 M-1 cm-1. They have strong luminescence in broad yellow-to-red region in solutions at room temperature. While chloro-substituent (complex 1) causes a little hypsochromic shift of the absorption maxima compared to unsubstituted 2, introduction of two methoxy-groups (complex 3) gives rise to a bathochromic shift of about 100 nm. Alternating current voltammetry studies of the complexes indicates reversible oxidation and reduction potentials. Calculated excited state oxidation potentials for 1-3 are negative enough to efficiently inject electrons into the conduction band of TiO2 (EF). 2014 Elsevier B.V. All rights reserved.
- Bezzubov, Stanislav I.,Doljenko, Vladimir D.,Troyanov, Sergey I.,Kiselev, Yuri M.
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- New bi-functional zinc catalysts based on robust and easy-to-handle N-chelating ligands for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions
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A series of novel zinc complexes were prepared by covalent linkage of various imidazolium-based ionic liquid moieties with the 2,2′-bipyridine ligand on the two sides of the 4,4′-position. The zinc(ii) complexes containing the rigid N-chelating ligand proved to be stable, highly efficient and easy-to-handle catalysts towards the synthesis of cyclic carbonate from epoxide and CO2 without the use of any co-catalyst or organic solvent. The catalysts can be easily recovered and reused without significant loss of activity and selectivity by control of the solvent. The kinetic study uncovered that the reaction was first-order with respect to the epoxide. Moreover, a plausible reaction mechanism was proposed, in which the zinc center could promote ring-opening of the epoxide for the synergetic effect with the anion X- in ILs. the Partner Organisations 2014.
- Luo, Rongchang,Zhou, Xiantai,Zhang, Wuying,Liang, Zhongxiu,Jiang, Jun,Ji, Hongbing
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supporting information
p. 4179 - 4189
(2014/09/30)
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- Dynamic combinatorial chemistry with novel dithiol building blocks: Towards new structurally diverse and adaptive screening collections
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We describe the synthesis of a range of novel dithiol-functionalized building blocks and demonstrate how they can be used to generate new structurally diverse dynamic combinatorial libraries. A proof-of-principle experiment using the catecholamine dopamine revealed that molecular recognition changed the library composition under biocompatible conditions and identified new promising candidate receptors of this biologically important neurotransmitter. Georg Thieme Verlag Stuttgart - New York.
- Postma, Tobias M.,Galloway, Warren R.J.D.,Cougnon, Fabien B. L.,Panto?, G. Dan,Stokes, Jamie E.,Spring, David R.
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supporting information
p. 765 - 769
(2013/05/09)
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- Study of asymmetric aldol and Mannich reactions catalyzed by proline-thiourea host-guest complexes in nonpolar solvents
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A proline-thiourea host-guest complex has been described as a good catalyst for asymmetric reactions such as aldol and Mannich reactions. High stereoselectivities were obtained under optimal conditions. Thiourea was observed to have an important effect on the reactivity and selectivity, even in an unconventional nonpolar reaction medium and without the need to utilize low temperatures. This proline-thiourea host-guest system has the ability to participate in a hydrogen bonding network.
- Demir, Ayhan Sitki,Basceken, Sinan
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p. 515 - 525
(2013/06/26)
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- Ruthenium complex dye with designed ligand capable of chelating triiodide anion for dye-sensitized solar cells
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Ru(4,4′-dicarboxyl-2,2′-bipyridine)[4,4′- bis(styrylaminocarbonyl)-2,2′-bipyridine](NCS)2, denoted as RuAS dye, was synthesized and well characterized by 1H-NMR, 13C-NMR, heteronuclear single quantum coherence, UV-vis and ESI-MS spectra. Its capability of chelating triiodide anions with the 4,4′-bis(styrylaminocarbonyl)-2,2′-bipyridine ligand, which was revealed by ATR-FTIR and 1H-NMR spectroscopies, reduced the charge recombination for dye-sensitized solar cells (DSSCs) by keeping the triiodide ions away from contact with the mesoporous TiO2 layer. Therefore, the open-circuit photovoltage of the DSSC barely changed with the triiodide concentration in the electrolyte. Moreover, the electron-withdrawing ability of the amide groups in the ligand increased the molar extinction coefficient of the dye, leading to the increase of photocurrent for DSSCs. The enhanced photovoltaic performance was further examined by incident photon-to-current conversion efficiency spectra, electrochemical impedance spectroscopy and open-circuit potential decay transient measurements.
- Ni, Jen-Shyang,Ho, Kuo-Chuan,Lin, King-Fu
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p. 3463 - 3470
(2013/07/05)
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- Simultaneous self-assembly of a [2]catenane, a trefoil knot, and a solomon link from a simple pair of ligands
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A topological triptych: Three molecular links, a [2]catenane, a trefoil knot, and a Solomon link, were obtained in one pot through the self-assembly of two simple ligands in the presence of ZnII (see picture). The approach relied on dynamic covalent chemistry and metal templation.
- Prakasam, Thirumurugan,Lusi, Matteo,Elhabiri, Mourad,Platas-Iglesias, Carlos,Olsen, John-Carl,Asfari, Zouhair,Cianferani-Sanglier, Sarah,Debaene, Francois,Charbonniere, Loic J.,Trabolsi, Ali
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p. 9956 - 9960
(2013/10/01)
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