- Molecular design of a novel ligand for Menshutkin complexation of Bi(iii) from aqueous acidic copper sulfate electrolyte solutions and experimental investigations
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5-Amino-2,9-diphenoxy-1,10-phenanthroline functionalized silica is designed to reversibly adsorb bismuth impurities from strongly acidic aqueous copper sulfate solutions. The ligand interacts with Bi(iii) ions through weak non-covalent interactions due to the presence of the arene-π electron cloud of the phenyl moiety. The stronger complexation of Bi(iii) as compared to Sb(iii), As(iii) and Cu(ii) ions with the ligand was explored using Density Functional Theory (DFT) under solvated conditions. The theoretical predictions were validated by experimental studies with Bi(iii)/Cu(ii) mixtures in aqueous acidic solutions. The ligand shows very high selectivity (α = 978) towards Bi(iii) in the presence of a high concentration of Cu(ii) in the acidic solutions.
- Arora, Jyotsna S.,Gaikar, Vilas G.
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- 1,10-phenanthrolinium ionic liquid crystals
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The 1,10-phenanthrolinium cation is introduced as a new building block for the design of ionic liquid crystals. 1,10-Phenanthroline, 5-methyl-1,10- phenanthroline, 5-chloro-1,10-phenanthroline, and 4,7-diphenyl-1,10- phenanthroline were quaternized by rea
- Cardinaels, Thomas,Lava, Kathleen,Goossens, Karel,Eliseeva, Svetlana V.,Binnemans, Koen
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- RuCp* complexes of ambidentate 4,5-diazafluorene derivatives: From linkage isomers to coordination-driven self-assembly
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The coordination chemistry of the {RuCp}+ fragment was studied toward several 4,5-diazafluorene derivatives. The ambidentate nature of these 4,5-diazafluorene derivatives with multiple coordination sites allowed for the syntheses of different linkage isomers and self-assembled macrocycles. Both a tetramer (2) and a monomer (3) of [RuCpL] (where L- = 4,5-diazafluorenide) were prepared with the L- ligand. The dimeric head-to-tail macrocycles [CpRu(LpH)]2Cl2 (4) and [CpRuLp]2 (5) were obtained with the ditopic L pH and Lp- ligands (where LpH = 9-(2-(diphenylphosphino)ethyl)-4,5-diazafluorene and Lp- = 9-(2-(diphenylphosphino)ethyl)-4,5-diazafluorenide). The bulky arene-substituted LMesH ligand (where LMesH = 3,6-dimesityl-4,5-diazafluorene) was prepared, and its coordination to {RuCp}+ gave [CpRu(LMesH)]Cl (13). The selective syntheses of different linkage isomers of [RuCp(LMes)] (14 and 15) (where LMes- = 3,6-dimesityl-4,5-diazafluorenide) were also demonstrated.
- Annibale, Vincent T.,Batcup, Rhys,Bai, Tao,Hughes, Sarah J.,Song, Datong
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- Synthesis and Characterization of a Ruthenium(II) Complex for the Development of Supramolecular Photocatalysts Containing Multidentate Coordination Spheres
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The synthesis of the new bis-heteroleptic RuII complex [(tbbpy)2Ru(dptpphz)](PF6)2 (7), that exhibits a tetradentate coordination sphere for a second metal centre, and its characterization are presented. The complex shows similar photostability and redox properties regarding the first ligand-centred reductions compared to its tpphz analogue. Concentration-dependent NMR investigations were performed and a dimerization constant (KD = 83 ± 5) could be calculated, which was significantly lower than that of other tpphz systems. Photophysical investigations reveal a stabilizing effect of the two electron-withdrawing 2-pyridyl substituents on π–π* transition of the phenazine sphere. The typical H2O-induced light-switch effects have also been observed. To further highlight the potential of the tetradentate coordination site, the ZnII adduct of 7 was prepared and preliminary studied.
- Huber, Fabian L.,Nauroozi, Djawed,Mengele, Alexander K.,Rau, Sven
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- Synthesis, Structure, Property, and Dinuclear Cu(II) Complexation of Tetraoxacalix[2]arene[2]phenanthrolines
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A number of novel tetraoxacalix[2]arene[2]phenanthrolines 7-11 containing phenanthroline and diverse aromatic linkages were conveniently synthesized by a one-pot protocol between a series of dihydroxy arenes and 1,10-phenanthroline derivatives. Single-crystal diffraction analysis revealed that the resulting macrocycles possess diverse conformational and cavity structures which are regulated by the different aromatic linkages. In line with the length of the aromatic linkages, the distance between the two phenanthroline moieties (dN-N) gradually increases from 6.92 to 13.30 ?, respectively. The physicochemical properties of these macrocyclic compounds were investigated by spectroscopic, CV, and DPV measurements. Owing to the coordination ability of the phenanthroline moieties and the tunable conformational structure, the macrocyclic hosts can form distinct dinuclear complexation with Cu2+. Typically, with a short aromatic linkage the 7b-2Cu(II) complex gives an O-bridged dicopper structure, while with long linkage the 11b-2Cu(II) complex possesses two discrete copper centers. The spectroscopic structure and the redox property of the dicopper complexes were investigated by XPS, CV, and DPV techniques. This work hence provides a platform to access biomimetic copper-containing small-molecule models with well-defined structures.
- Wang, Xue-Yuan,Ao, Yu-Fei,Wang, Qi-Qiang,Wang, De-Xian
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- Template construction of a series of supramolecular coordination polymers via 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium cation
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Five cation-induced complexes, (phen-dzp) [ZnBr3N3] (1), (phen-dzp) [ZnCl2Br2] (2), (phen-dzp) (H 3O)2 [Fe(CN)6] (3), (phen-dzp)2 [Cu2I6] (4), and [(phen-dzp)(Ag2Br 4)]n (5) [phen-dzp = (C15H14N 2)2+, 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10] phenanthroline-4,8-diium], have been synthesized via self-assembly in solution. The crystal structures of 1-3 show that they all crystallize in monoclinic systems with mononuclear structures. Compound 4 is a binuclear coordination polymer. Complex 5 possesses a 2-D supramolecular layer with the organic cation phen-dzp trapped in it; interestingly, each inorganic polymeric planar layer is composed of large, decagon rings formed by sharing four Br- and four [Ag2Br4] quadrilateral units with six adjacent decagon rings. The results provide insights into template effects of synthetic approaches on the construction of supramolecular compounds. The structures of 1-5 have been characterized by elemental analysis, infrared spectra, and single-crystal X-ray crystallography. Solid-state photoluminescence properties of 1-5 have been determined.
- Zhang, Zhenhua,Niu, Yunyin,Ng, Seikweng,Wu, Benlai,Hou, Hongwei
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- Revisiting the IspH catalytic system in the deoxyxylulose phosphate pathway: Achieving high activity
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(Chemical Equation Presented) From two C5 isoprene building blocks, isopentenyl diphosphate (IPP) and its isomer dimethylallyl diphosphate (DMAPP), the more than 30000 members of the isoprenoid family are constructed in nature using two biosynthetic pathways, the mevalonate (MVA) pathway and the deoxyxylulose phosphate (DXP) pathway. IspH of the DXP pathway is a protein containing an iron-sulfur cluster and catalyzes a reductive dehydration reaction of the DXP pathway. In the literature, a wide range of Escherichia coli IspH activities have been reported (2.0 nmol min-1 mg-1 to 3.4 μmol min-1 mg-1). For such a broad range of activities, reaction assays were carried out under many different conditions, preventing direct comparison of the activities and determination of the key factor responsible for such a dramatic difference in IspH activities. In this work, we systematically examined the role of redox mediators in IspH catalysis using E. coli IspH as the enzyme and dithionite as the ultimate electron source. Our studies not only suggest the importance of the iron-sulfur cluster but also improve the E. coli IspH activity by nearly 97-fold relative to that from the E. coli NADPH-flavodoxin reductase-flavodoxin system.
- Xiao, Youli,Chu, Lisa,Sanakis, Yiannis,Liu, Pinghua
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- A Ligand That Targets CUG Trinucleotide Repeats
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The development of small molecules that can recognize specific RNA secondary and tertiary structures is currently an important research topic for developing tools to modulate gene expression and therapeutic drugs. Expanded CUG trinucleotide repeats, known as toxic RNA, capture the splicing factor MBNL1 and are causative of neurological disorder myotonic dystrophy type 1 (DM1). Herein, the rational molecular design, synthesis, and binding analysis of 2,9-diaminoalkyl-substituted 1,10-phenanthroline (DAP), which bound to CUG trinucleotide repeats, is described. The results of melting temperature (Tm) analyses, surface plasmon resonance (SPR) assay, and electrospray spray ionization time-of-flight (ESI-TOF) mass spectrometry showed that DAP bound to r(CUG)9but not to r(CAG)9and r(CGG)9. The dual luciferase assay clearly indicated DAP bound to the r(CUG)nrepeat by affecting the translation in vitro.
- Li, Jinxing,Matsumoto, Jun,Bai, Li-Ping,Murata, Asako,Dohno, Chikara,Nakatani, Kazuhiko
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- Torands revisited: Metal sequestration and self-assembly of cyclo-2,9-tris-1,10-phenanthroline hexaaza macrocycles
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A series of novel toroidal cyclo-2,9-tris-1,10-phenanthroline macrocycles with an unusual hexaaza cavity are reported. Nickel-mediated Yamamoto aryl-aryl coupling was found to be a versatile tool for the cyclotrimerization of functionalized 1,10-phenathroline precursors. Due to the now improved processability, both liquid-crystalline behavior in the bulk phase and two-dimensional self-assembly at the molecular level could be studied, for the first time, for a torand system. The macrocycles exhibited a strong affinity for the complexation of different metal cations, as evidenced by MALDI-TOF analysis and spectroscopic methods. Experimental results were correlated to an extensive computational study of the cyclo-2,9-tris-1,10-phenanthroline cavity and its binding mode for metal cations. Due to the combination of several interesting features, toroidal macrocycles may find future applications in the field of ion and charge transport through molecular channels, as well as for chemical sensing and molecular writing in surface-confined monolayers under STM conditions.
- Schwab, Matthias Georg,Takase, Masayoshi,Mavrinsky, Alexey,Pisula, Wojciech,Feng, Xinliang,Gámez, José A.,Thiel, Walter,Mali, Kunal S.,De Feyter, Steven,Müllen, Klaus
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- Highly Ordered, Self-Assembled Monolayers of a Spin-Crossover Complex with In-Plane Interactions
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For the technological integration of molecular switches in electronic devices, self-assembling nanomaterials of such switches are highly sought after. The syntheses of a new tetrapyridyl ligand bearing a C12 alkyl chain and two N?H bridges (compound 1) and of its iron(II) complex [Fe(1)(NCS)2] (compound 2), are described. Magnetic susceptibility data for bulk samples of 2 confirmed their gradual spin-crossover properties. The self-assembly of 1 and 2 on highly ordered pyrolytic graphite surfaces (HOPG) was investigated by Scanning Tunneling Microscopy (STM). Both compounds 1 and 2 formed ordered monolayers after deposition by drop casting. The patterns of the two compounds are very different, which is attributed to the fundamentally different hydrogen bonding networks before and after coordination of Fe(NCS)2 to the tetradentate chelate. Two possible models for the self-assembly of 1 and 2 are provided. This work suggests that it is possible to design molecular switches that self-assemble on surfaces in highly ordered monolayer films. This is a significant step in the development of spin-switching materials, which may streamline the integration of molecular switches in for example memory and sensing devices.
- Bonnet, Sylvestre,Spa, Silvia,Zheng, Sipeng,van Geest, Erik P.,van Ruitenbeek, Jan M.
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p. 2814 - 2821
(2021/07/07)
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- Cu-tethered macrocycle catalysts: Synthesis and size-selective CO2-fixation to propargylamines under ambient conditions
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A novel air-stable, Cu-tethered macrocycle catalyst possessing a large inner cavity was successfully synthesized, creating a unique supramolecular catalytic system. The catalyst was utilized in the CO2-fixation reaction to propargylamines. The reaction proceeded more efficiently compared to the conventional CuI catalyst under atmospheric CO2 condition. Notably, owing to its topological effect, the Cu-tethered macrocycle catalyst exhibited unique substrate size selectivity.
- Kim, Nam-Kyun,Sogawa, Hiromitsu,Takata, Toshikazu
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supporting information
(2020/05/01)
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- Ligand-Controlled Product Selectivity in Electrochemical Carbon Dioxide Reduction Using Manganese Bipyridine Catalysts
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Electrocatalysis is a promising tool for utilizing carbon dioxide as a feedstock in the chemical industry. However, controlling the selectivity for different CO2 reduction products remains a major challenge. We report a series of manganese carbonyl complexes with elaborated bipyridine or phenanthroline ligands that can reduce CO2 to either formic acid, if the ligand structure contains strategically positioned tertiary amines, or CO, if the amine groups are absent in the ligand or are placed far from the metal center. The amine-modified complexes are benchmarked to be among the most active catalysts for reducing CO2 to formic acid, with a maximum turnover frequency of up to 5500 s-1 at an overpotential of 630 mV. The conversion even works at overpotentials as low as 300 mV, although through an alternative mechanism. Mechanistically, the formation of a Mn-hydride species aided by in situ protonated amine groups was determined to be a key intermediate by cyclic voltammetry, 1H NMR, DFT calculations, and infrared spectroelectrochemistry.
- R?nne, Magnus H.,Cho, Dasol,Madsen, Monica R.,Jakobsen, Joakim B.,Eom, Seunghwan,Escoudé, émile,Hammersh?j, Hans Christian D.,Nielsen, Dennis U.,Pedersen, Steen U.,Baik, Mu-Hyun,Skrydstrup, Troels,Daasbjerg, Kim
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supporting information
p. 4265 - 4275
(2020/03/05)
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- BIS-PHENANTHROLINE IRON MACROCYCLE COMPLEX FOR OXYGEN REDUCTION REACTION
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Disclosed are compounds, compositions, and methods useful for the oxygen reduction reaction (ORR) and capable of operating efficiently at low overpotentials.
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Page/Page column 6; 48
(2020/09/27)
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- 2,9-dipyridyl-1,10-phenanthroline derivatives useful as actinide ligands, method for synthesizing same, and uses thereof
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The invention relates to novel compounds useful as ligands of actinides and which meet general formula (I) hereinafter: where: R1 and R2=H, a C1 to C12 hydrocarbon group, a monocyclic aryl or aryl-(C1 to C6)alkyl group;R3, R4, R5 and R6=H; a C1 to C12 hydrocarbon group; a monocyclic aryl or aryl-(C1 to C6)alkyl group; a —NR7R8 or —NR7COR8 group where R7=H, a C1 to C12 hydrocarbon group, a monocyclic aryl or aryl-(C1 to C6)alkyl group, while R8=a C1 to C12 hydrocarbon group, a monocyclic aryl or aryl-(C1 to C6)alkyl group; an —OR9 or —SR9 group where R9=a C1 to C12 hydrocarbon group, a monocyclic C6 aryl or aryl-(C1 to C6)alkyl group. A further subject of the invention is a method for synthesizing these compounds and the uses thereof.
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Page/Page column 8
(2015/07/15)
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- 1,10-phenanthroline and non-symmetrical 1,3,5-triazine dipicolinamide-based ligands for group actinide extraction
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The synthesis and evaluation of new extractants for spent nuclear fuel reprocessing are described. New bitopic ligands constituted of phenanthroline and 1,3,5-triazine cores functionalized by picolinamide groups were designed. Synthetic routes were investigated and optimized to obtain twelve new polyaza-heterocyclic ligands. In particular, an efficient and versatile methodology was developed to access non-symmetric 2-substituted-4,6-di(6- picolin-2-yl)-1,3,5-triazines from the 1,3,5-triazapentadiene precursor in the presence of anhydride reagents. Extraction studies showed the ability of both ligand series to extract and separate actinides selectively at different oxidation states (UVI, NpV,VI, AmIII, Cm III, and PuIV) from an acidic solution (3 M HNO 3). Phenanthroline-based ligands show the most promising efficiency for use in the group actinide extraction (GANEX) process due to a higher number of donor nitrogen atoms and a suitable pre-organization of the dipicolinamide-1,10-phenanthroline architecture. Actinides/lanthanides extraction: The synthesis and evaluation of new bitopic ligands constituted of poly-aza-aromatic units functionalized by amide groups for spent nuclear fuel reprocessing is described. Original synthetic routes were investigated to obtain the ligands (see figure).
- Bisson, Julia,Dehaudt, Jeremy,Charbonnel, Marie-Christine,Guillaneux, Denis,Miguirditchian, Manuel,Marie, Cecile,Boubals, Nathalie,Dutech, Guy,Pipelier, Muriel,Blot, Virginie,Dubreuil, Didier
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p. 7819 - 7829
(2014/07/07)
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- Towards allosteric receptors synthesis of β-cyclodextrin- functionalised 2,2'-bipyridines and their metal complexes
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Herein, we present three new 2,2'-bipyridines that carry two β-cyclodextrin moieties in different substitution patterns. When coordinated by zinc(II) or copper(I) ions (or their complexes), these compounds undergo conformational changes and switch between
- Kremer, Christopher,Schnakenburg, Gregor,Lutzen, Arne
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p. 814 - 824
(2014/05/06)
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- Organic and organometallic nanofibers formed by supramolecular assembly of diamond-shaped macrocyclic ligands and PdII complexes
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Stacked rings: A diamond-shaped macrocycle with two inward phenanthroline ligands and outward long alkyl chains, and its PdII complex form organic and organometallic fibrous aggregates, respectively, as revealed by NMR, UV/Vis, AFM, and TEM measurements. The most likely structures are face-to-face stacked macrocycles, generating nanotubes.
- Kuritani, Masumi,Tashiro, Shohei,Shionoya, Mitsuhiko
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supporting information
p. 1368 - 1371
(2013/07/26)
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- Direct arylation of phenanthroline derivatives via oxidative C-H/C-H cross-coupling: Synthesis and discovery of excellent ligands
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A concise synthetic protocol for aryl functionalized phenanthrolines has been developed. It was demonstrated that 3,8-diphenyl-1,10-phenanthroline (7a) is competent in promoting transition-metal-free direct arylation and 2,3,8,9-tetraphenyl-1,10-phenanthroline (8a) is a highly efficient ligand in the in situ Pd-catalysed Heck reaction.
- Li, Bijin,Qin, Xurong,You, Jingsong,Cong, Xuefeng,Lan, Jingbo
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supporting information
p. 1290 - 1293
(2013/05/09)
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- Expanded π-electron systems, tri(phenanthro)hexaazatriphenylenes and tri(phenanthrolino)hexaazatriphenylenes, that are self-assembled to form one-dimensional aggregates
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This paper reports the self-assembling and electrochemical nature of hexaazatriphenylene-based electron-deficient heteroaromatics with an expanded π-electron system. The tri(phenanthro)hexaazatriphenylenes (TPHAT-Cs) and tri(phenanthrolino)hexaazatriphenylenes (TPHAT-Ns) were prepared by condensation reactions of the corresponding phenanthrenequinones and phenanthrolinediones, respectively, with hexaaminobenzene. Their electron affinity was indicated from cyclic voltammetry measurements, in which the first reduction potentials were evaluated at around -1.7 V (vs Fc/Fc+) in dichloromethane. In nonpolar and polar solvents and in the film state, the TPHAT-Cs and TPHAT-Ns formed one-dimensional aggregates with an H-type parallel stacking mode. In the MALDI-TOF mass spectra, significant peaks were seen at several multiples of the parent ion up to tetramer aggregates. The 1H NMR spectra indicated a line-broadening effect due to the aggregation. The UV-vis and fluorescence spectra showed a concentration dependence, which is attributed to a dynamic exchange between the monomer and aggregate species. The order of the aggregative nature was estimated from the concentration dependence and the fluorescence quantum yield. By replacement of the peripheral aromatic moieties instead of the phenanthrene (TPHAT-Cs) with the phenanthroline (TPHAT-Ns), the aggregative nature was enhanced.
- Ishi-I, Tsutomu,Hirashima, Ryoichi,Tsutsumi, Naotaka,Amemori, Shogo,Matsuki, Shigeki,Teshima, Yuuki,Kuwahara, Rempei,Mataka, Shuntaro
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scheme or table
p. 6858 - 6868
(2010/11/24)
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- Concave 1,10-phenanthrolines as ligands for cyclopropanations - Towards a deeper understanding of the stereoselectivity
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Four new mono- and bimacrocyclic 1,10-phenanthrolines - 3b and 4a-c - containing aryl bridgeheads have been synthe- sised. The etherification of the aryl bridgeheads was accomplished by Williamson or Mitsunobu reactions. A key step in the synthesis of the macrocyclic phenanthrolines 3 and 4 is the Suzuki coupling of 2,9-diiodo-1,10-phenan- throline (12) with the appropriately substituted boronic acids 17 and 20. Ring-closing metathesis and hydrogenation completed the synthesis. The resulting macrocyclic 1,10-phenan- throlines 3b and 4a-c were tested as ligands in a copper(I)- catalysed stereoselective cyclopropanation.
- Eggers, Friederike,Luening, Ulrich
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scheme or table
p. 2328 - 2341
(2009/09/05)
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- Synthesis of a bis-macrocycle containing two back-to-back rigidly connected 1,10-phenanthroline units as a central core and its incorporation in a handcuff-like catenane
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A bis-macrocycle containing two back-to-back connected 1,10-phenanthroline chelates has been prepared. The synthetic strategy involves the preparation of a monocyclic precursor consisting of a 1,10-phenanthroline5,6-dione fragment incorporated in a 30-mem
- Frey, Julien,Kraus, Tomas,Heitz, Valerie,Sauvage, Jean-Pierre
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p. 7584 - 7594
(2008/03/14)
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