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1.
Strong Antiferromagnetic Coupling of Spins in the (MDABCO+)(C60.−) Salt with 3D Close Packing of the C60.− Radical Anions (MDABCO+: N‐Methyldiazabicyclooctanium Cation)
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Dr. Dmitri V. Konarev Dr. Salavat S. Khasanov Dr. Akihiro Otsuka Prof. Hideki Yamochi Prof. Gunzi Saito Prof. Rimma N. Lyubovskaya 《化学:亚洲杂志》2014,9(6):1629-1635
A new salt, (MDABCO+)(C60.?) ( 1 ; MDABCO+=N‐methyldiazabicyclooctanium cation), was obtained as single crystals. The crystal structure of 1 determined at 250 and 100 K showed 3D close packing of fullerenes with eight fullerene neighbors for each C60.?. These neighbors are located at 10.01–10.11 Å center‐to‐center distances (250 K) and van der Waals interfullerene C???C contacts are formed with four fullerene neighbors arranged in the bc plane. Fullerene ordering observed below 160 K is accompanied by the appearance of one and a half independent C60.? and trebling of the unit cell along the b axis. Fullerenes are packed closer to each other at 100 K. As a result, fullerenes are located in the three‐dimensional packing at 9.91–10.12 Å center‐to‐center distances and 18 short interfullerene C???C contacts are formed for each C60.?. Although they are closed packed, fullerenes are not dimerized down to 1.9 K. Magnetic data indicate strong antiferromagnetic coupling of spins in the 70–300 K range with a Weiss temperature of Θ=?118 K. Magnetic susceptibility shows a round maximum at 46 K. Such behavior can be described well by the Heisenberg model for square two‐dimensional antiferromagnetic coupling of spins with an exchange interaction of J/kB=?25.3 K. This magnetic coupling is one of the strongest observed for C60.? salts. 相似文献
2.
Metallic and Mott Insulating Spin‐Frustrated Antiferromagnetic States in Ionic Fullerene Complexes with a Two‐Dimensional Hexagonal C60.− Packing Motif
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Dr. Dmitri V. Konarev Dr. Salavat S. Khasanov Dr. Akihiro Otsuka Dr. Mitsuhiko Maesato Dr. Mikio Uruichi Dr. Kyuya Yakushi Dr. Artem F. Shevchun Prof. Dr. Hideki Yamochi Prof. Dr. Gunzi Saito Prof. Rimma N. Lyubovskaya 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7268-7277
(MDABCO+)(C60.?)(TPC) ( 1 ), in which MDABCO+ is N‐methyldiazabicyclooctanium, TPC is triptycene, and both have threefold symmetry, is a rare example of a fullerene‐based quasi‐2D metal and contains closely packed hexagonal fullerene layers with interfullerene center‐to‐center distances of 10.07 Å at 300 K. Evidence for the metallic nature of 1 was obtained by optical and microwave conductivity measurements on single crystals. The metal is characterized by a nontypical Drude response and relatively large optical mass (m*/m0=6.7). The latter indicates a narrow‐band nature, which is consistent with the calculated bandwidth of 0.10–0.15 eV. The coexistence of metallic and antiferromagnetic nonmetallic 2D layers was observed in 1 above 200–230 K. It was assumed that the nonmetallic layers undergo a transition to the metallic state below 200 K due to ordering of the fullerene and cationic sublattices. New layered complex (MQ+)(C60.?)(TPC) ( 2 ) with a hexagonal arrangement of C60.? was obtained by increasing the interfullerene distance with the bulkier N‐methylquinuclidinium cations (MQ+) having threefold symmetry. The structure of 2 is characterized by increased interfullerene center‐to‐center distances in the layers (10.124, 10.155, and 10.177 Å at 250 K). Unit‐cell doubling parallel to the 2D layer (along the b axis) was observed at low temperatures. In contrast to metallic 1 , 2 exhibits a nonmetallic spin‐frustrated state with an antiferromagnetic interaction of spins (the Weiss temperature is ?27 K) and no magnetic ordering down to 1.9 K. It was supposed that the expanded interfullerene distances in the triangular arrangement decrease the bandwidth and suppress metallic conductivity in 2 , and thus a Mott–Hubbard insulating state with antiferromagnetically frustrated spins results. 相似文献
3.
Magnetic Coupling and Optical Properties of the S6‐Dodecakis(trifluoromethyl)fullerene Radical Anions in the Layered Salt (PPN+)[C60(CF3)12.−]
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Dr. Dmitri V. Konarev Dr. Natalia A. Romanova Roman A. Panin Dr. Alexey A. Goryunkov Prof. Sergey I. Troyanov Prof. Rimma N. Lyubovskaya 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5380-5387
Poly(trifluoromethyl)fullerene S6‐C60(CF3)12 was reduced by sodium fluorenone ketyl in the presence of (PPN)Cl (PPN=bis(triphenylphosphine)iminium) to afford the salt (PPN)[C60(CF3)12] ( 1 ), which contains C60(CF3)12.? radical anions. In the crystal structure of 1 , C60(CF3)12.? layers alternate with the PPN+ cations. There are short F ??? F contacts between C60(CF3)12.? radical anions within the layers but no C ??? C contacts. DFT calculations revealed that the negative charge on C60(CF3)12.? is distributed mainly between sp2 carbon and fluorine atoms, whereas spin density is localized mainly on the fullerene‐cage sp2 carbon atoms. IR and UV/Vis/NIR spectra in the solid state and solution showed characteristic changes relative to those of neutral S6‐C60(CF3)12 due to the formation of radical anions. The solid‐state electronic spectrum of 1 exhibits a single broad band at 738 nm attributed to C60(CF3)12.?. Crystals of 1 show a narrow EPR signal with g=2.0025 (ΔH=0.45 mT) at 300 K. The temperature dependence of the integral intensity follows the Curie–Weiss law with a negative Weiss temperature of ?11.8 K (30–300 K) indicating antiferromagnetic interaction of spins. This dependence was approximated by the Heisenberg model for one‐dimensional chains of antiferromagnetically interacting spins with exchange interaction J/kB=?9.1 K. It was assumed that magnetic interaction between the C60(CF3)12.? spins in the layers is mediated by short F ??? F contacts. 相似文献
4.
Dr. Dmitri V. Konarev Prof. Sergey I. Troyanov Dr. Salavat S. Khasanov Dr. Akihiro Otsuka Prof. Hideki Yamochi Prof. Gunzi Saito Prof. Rimma N. Lyubovskaya 《化学:亚洲杂志》2013,8(6):1139-1143
A new salt, (PPN+)2(C702?) ? 2 C6H4Cl2 ( 1 ), which contains C702? dianions, has been obtained as single crystals (PPN+=bis(triphenylphosphine)iminium cation). The C702? dianions form polymeric zigzag (C702?)n chains, in which the fullerene units are bonded through single C? C bonds of length 1.581(5)–1.586(6) Å. The distance between the centers of neighboring C702? units is 10.441 Å. The optical and magnetic properties of (C702?)n have also been studied. Decreasing the symmetry of C70 in the polymer activate about 20 new IR bands in addition to the 10 IR‐active bands of the starting C70. The polymeric structure shows absorptions in the visible and NIR regions, with three main bands at 890, 1200, and 1550 nm, instead of one band of isolated C702? dianions at 1165–1184 nm. We concluded that the (C702?)n polymer was diamagnetic, with a negative molar magnetic susceptibility of ?3.82×10?4 emu mol?1 per C702? dianion. The polymer is EPR silent and a weak narrow EPR signal in salt 1 is due to impurities, which only constitute 0.84 % of spin S=1/2 of the total amount of fullerene C70. 相似文献
5.
Dmitri V. Konarev Alexey V. Kuzmin Salavat S. Khasanov Alexey A. Goryunkov Victor A. Brotsman Ilya N. Ioffe Akihiro Otsuka Hideki Yamochi Hiroshi Kitagawa Rimma N. Lyubovskaya 《化学:亚洲杂志》2019,14(11):1958-1964
Radical anion salt {cryptand[2.2.2] (K+)}2(bispheroid)2??3.5C6H4Cl2 ( 1 ) of the double‐caged fullerene C60 derivative, in which fullerene cages are linked by a cyclobutane bridging cycle and additionally by a pyrrolizidine moiety, was obtained. Each fullerene cage in this derivative accepts one electron on reduction, thus forming the (bispheroid)2? dianions with two interacting S=1/2 spins on the neighboring cages. Low‐temperature magnetic measurements reveal a singlet ground state of the bispheroid dianions whereas triplet contributions prevail at increased temperature. An estimated exchange interaction between two spins J/kB=?78 K in 1 indicates strong magnetic coupling between them, nearly two times higher than that (J/kB=?44.7 K) in previously studied (C60?)2 dimers linked via a cyclobutane bridge only. The enhancement of magnetic coupling in 1 can be explained by a shorter distance between the fullerene cages and, possibly, an additional channel for the magnetic exchange provided by a pyrrolizidine bridge. Quantum‐chemical calculations of the lowest electronic state of the dianions by means of multi‐configuration quasi‐degenerate perturbation theory support the experimental findings. 相似文献
6.
Radical copolymerization of fullerene (C60) and n‐butyl methacrylate (BMA) has been carried out using triphenylbismuthonium ylide as an initiator at 70°C for 4 h in a dilatometer under nitrogen atmosphere. The kinetic expression of the polymerization is Rpα [Ylide]0.5[C60]?1.0[BMA]1.2, which is similar to that expected for ideal kinetics. The rate of polymerization increases with an increase in the concentration of initiator and BMA. However, it decreases with an increase in the concentration of fullerene. Fullerene acts as radical scavengers causing retardation in polymerization. The activation energy of copolymerization was estimated to be 72.2 K J mol?1. The fullerene‐containing BMA copolymers were characterized by FTIR, 1H NMR, 13C NMR, UV–vis, and GPC analyses. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 608–619, 2011 相似文献
7.
Tribenzotriquinacene Receptors for C60 Fullerene Rotors: Towards C3 Symmetrical Chiral Stators for Unidirectionally Operating Nanoratchets
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Dr. Björn Bredenkötter Dr. Maciej Grzywa Dr. Mohammad Alaghemandi Dr. Rochus Schmid Prof. Dr. Wouter Herrebout Prof. Dr. Patrick Bultinck Prof. Dr. Dirk Volkmer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):9100-9110
The synthesis of a stereochemically pure concave tribenzotriquinacene receptor ( 7 ) for C60 fullerene, possessing C3 point group symmetry, by threefold condensation of C2‐symmetric 1,2‐diketone synthons ( 5 ) and a hexaaminotribenzotriquinacene core ( 6 ) is described. The chiral diketone was synthesized in a five‐step reaction sequence starting from C2h‐symmetric 2,6‐di‐tert‐butylanthracene. The highly diastereo‐discriminating Diels–Alder reaction of 2,6‐di‐tert‐butylanthracene with fumaric acid di(?)menthyl ester, catalyzed by aluminium chloride, is the relevant stereochemistry introducing step. The structure of the fullerene receptor was verified by 1H and 13C NMR spectroscopy, mass spectrometry and single crystal X‐ray diffraction. VCD and ECD spectra were recorded, which were corroborated by ab initio DFT calculations, establishing the chiral nature of 7 with about 99.7 % ee, based on the ee (99.9 %) of the chiral synthon ( 1 ). The absolute configuration of 7 could thus be established as all‐S [(2S,7S,16S,21S,30S,35S)‐( 7 )]. Spectroscopic titration experiments reveal that the host forms 1:1 complexes with either pure fullerene (C60) or fullerene derivatives, such as rotor 1′‐(4‐nitrophenyl)‐3′‐(4‐N,N‐dimethylaminophenyl)‐pyrazolino[4′,5′:1,2][60]fullerene ( R ). The complex stability constants of the complexes dissolved in CHCl3/CS2 (1:1 vol. %) are K([ C60 ? 7 ])=319(±156) M ?1 and K([ R ? 7 ])=110(±50) M ?1. With molecular dynamics simulations using a first‐principles parameterized force field the asymmetry of the rotational potential for [ R ? 7 ] was shown, demonstrating the potential suitability of receptor 7 to act as a stator in a unidirectionally operating nanoratchet. 相似文献
8.
Wen‐Jing Shi Dr. Mohamed E. El‐Khouly Dr. Kei Ohkubo Prof. Shunichi Fukuzumi Prof. Dennis K. P. Ng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11332-11341
An efficient functional mimic of the photosynthetic antenna‐reaction center has been designed and synthesized. The model contains a near‐infrared‐absorbing aza‐boron‐dipyrromethene (ADP) that is connected to a monostyryl boron‐dipyrromethene (BDP) by a click reaction and to a fullerene (C60) using the Prato reaction. The intramolecular photoinduced energy and electron‐transfer processes of this triad as well as the corresponding dyads BDP‐ADP and ADP‐C60 have been studied with steady‐state and time‐resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge‐separated states. Such calculations show that electron transfer from the singlet excited ADP (1ADP*) to C60 yielding ADP.+‐C60.? is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from 1BDP* to ADP in the dyad BDP‐ADP and electron transfer from 1ADP* to C60 in the dyad ADP‐C60. Sequential energy and electron transfer have also been clearly observed in the triad BDP‐ADP‐C60. By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈1011 s?1). The dynamics of electron transfer through 1ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge‐separation process from 1ADP* to C60 has been detected, which gives the relatively long‐lived BDP‐ADP.+C60.? with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge‐separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP‐ADP and ADP‐C60, and the triad BDP‐ADP‐C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems. 相似文献
9.
Dr. Dipanwita Das Hemlata Agarwala Dr. Abhishek Dutta Chowdhury Tuhin Patra Dr. Shaikh M. Mobin Prof. Dr. Biprajit Sarkar Prof. Dr. Wolfgang Kaim Prof. Dr. Goutam Kumar Lahiri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7384-7394
The complex series [Ru(pap)(Q)2]n ([ 1 ]n–[ 4 ]n; n=+2, +1, 0, ?1, ?2) contains four redox non‐innocent entities: one ruthenium ion, 2‐phenylazopyridine (pap), and two o‐iminoquinone moieties, Q=3,5‐di‐tert‐butyl‐N‐aryl‐1,2‐benzoquinonemonoimine (aryl=C6H5 ( 1+ ); m‐(Cl)2C6H3 ( 2+ ); m‐(OCH3)2C6H3 ( 3+ ); m‐(tBu)2C6H3 ( 4 +)). A crystal structure determination of the representative compound, [ 1 ]ClO4, established the crystallization of the ctt‐isomeric form, that is, cis and trans with respect to the mutual orientations of O and N donors of two Q ligands, and the coordinating azo N atom trans to the O donor of Q. The sensitive C? O (average: 1.299(3) Å), C? N (average: 1.346(4) Å) and intra‐ring C? C (meta; average: 1.373(4) Å) bond lengths of the coordinated iminoquinone moieties in corroboration with the N?N length (1.292(3) Å) of pap in 1 + establish [RuIII(pap0)(Q.?)2]+ as the most appropriate electronic structural form. The coupling of three spins from one low‐spin ruthenium(III) (t2g5) and two Q.? radicals in 1 +– 4 + gives a ground state with one unpaired electron on Q.?, as evident from g=1.995 radical‐type EPR signals for 1 +– 4 +. Accordingly, the DFT‐calculated Mulliken spin densities of 1 + (1.152 for two Q, Ru: ?0.179, pap: 0.031) confirm Q‐based spin. Complex ions 1 +– 4 + exhibit two near‐IR absorption bands at about λ=2000 and 920 nm in addition to intense multiple transitions covering the visible to UV regions; compounds [ 1 ]ClO4–[ 4 ]ClO4 undergo one oxidation and three separate reduction processes within ±2.0 V versus SCE. The crystal structure of the neutral (one‐electron reduced) state ( 2 ) was determined to show metal‐based reduction and an EPR signal at g=1.996. The electronic transitions of the complexes 1 n– 4 n (n=+2, +1, 0, ?1, ?2) in the UV, visible, and NIR regions, as determined by using spectroelectrochemistry, have been analyzed by TD‐DFT calculations and reveal significant low‐energy absorbance (λmax>1000 nm) for cations, anions, and neutral forms. The experimental studies in combination with DFT calculations suggest the dominant valence configurations of 1 n– 4 n in the accessible redox states to be [RuIII(pap0)(Q.?)(Q0)]2+ ( 1 2+– 4 2+)→[RuIII(pap0)(Q.?)2]+ ( 1 +– 4 +)→[RuII(pap0)(Q.?)2] ( 1 – 4 )→[RuII(pap.?)(Q.?)2]? ( 1 ?– 4 ?)→[RuIII(pap.?)(Q2?)2]2? ( 1 2?– 4 2?). 相似文献
10.
Kyosuke Matsumoto Shunsuke Kusaba Yuya Tanaka Yoshihisa Sei Munetaka Akita Kazushi Aritani Masa‐aki Haga Michito Yoshizawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(25):8551-8555
Synthesis of molecular containers capable of incorporating multiple fullerenes remains challenging. Reported here is that room‐temperature mixing of metal ions with W‐shaped bispyridine ligands featuring polyaromatic panels results in the quantitative formation of a peanut‐shaped M2L4 capsule. The capsule reversibly converts into two molecules of an ML2 double tube in response to changes in the solvent. Notably, the capsule allows the incorporation of two fullerene molecules into the connected two spherical cavities at room temperature. The close proximity yet non‐contact of the encapsulated C60 molecules, with a separation of 6.4 Å, was revealed by X‐ray crystallographic analysis. The resultant, unusual fullerene dimer undergoes sequential reduction within the capsule to generate (C60.?)2, C60.??C602?, and (C602?)2 species. Furthermore, temperature‐controlled stepwise incorporation of two C60 molecules into the capsule is demonstrated. 相似文献
11.
Venugopal Bandi Dr. Mohamed E. El‐Khouly Dr. Kei Ohkubo Dr. Vladimir N. Nesterov Prof. Melvin E. Zandler Prof. Shunichi Fukuzumi Prof. Francis D'Souza 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7221-7230
Donor–acceptor distance, orientation, and photoexcitation wavelength are key factors in governing the efficiency and mechanism of electron‐transfer reactions both in natural and synthetic systems. Although distance and orientation effects have been successfully demonstrated in simple donor–acceptor dyads, revealing excitation‐wavelength‐dependent photochemical properties demands multimodular, photosynthetic‐reaction‐center model compounds. Here, we successfully demonstrate donor– acceptor excitation‐wavelength‐dependent, ultrafast charge separation and charge recombination in newly synthesized, novel tetrads featuring bisferrocene, BF2‐chelated azadipyrromethene, and fullerene entities. The tetrads synthesized using multistep synthetic procedure revealed characteristic optical, redox, and photo reactivities of the individual components and featured “closely” and “distantly” positioned donor–acceptor systems. The near‐IR‐emitting BF2‐chelated azadipyrromethene acted as a photosensitizing electron acceptor along with fullerene, while the ferrocene entities acted as electron donors. Both tetrads revealed excitation‐wavelength‐dependent, photoinduced, electron‐transfer events as probed by femtosecond transient absorption spectroscopy. That is, formation of the Fc+–ADP–C60.? charge‐separated state upon C60 excitation, and Fc+–ADP.?–C60 formation upon ADP excitation is demonstrated. 相似文献
12.
Site‐Directed Dimerization of Bowl‐Shaped Radical Anions to Form a σ‐Bonded Dibenzocorannulene Dimer
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Dr. Sarah N. Spisak Dr. Alexander V. Zabula Melisa Alkan Dr. Alexander S. Filatov Prof. Dr. Andrey Yu. Rogachev Prof. Dr. Marina A. Petrukhina 《Angewandte Chemie (International ed. in English)》2018,57(21):6171-6175
Designed site‐directed dimerization of the monoanion radicals of a π‐bowl in the solid state is reported. Dibenzo[a,g]corannulene (C28H14) was selected based on the asymmetry of the charge/spin localization in the C28H14.? anion. Controlled one‐electron reduction of C28H14 with Cs metal in diglyme resulted in crystallization of a new dimer, [{Cs+(diglyme)}2(C28H14?C28H14)2?] ( 1 ), as revealed by single crystal X‐ray diffraction study performed in a broad range of temperatures. The C?C bond length between two C28H14.? bowls (1.560(8) Å) measured at ?143 °C does not significantly change upon heating of the crystal to +67 °C. The single σ‐bond character of the C?C linker is confirmed by calculations. The trans‐disposition of two bowls in 1 is observed with the torsion angles around the central C?C bond of 172.3(5)° and 173.5(5)°. A systematic theoretical evaluation of dimerization pathways of C28H14.? radicals confirmed that the trans‐isomer found in 1 is energetically favored. 相似文献
13.
《Electroanalysis》2005,17(24):2217-2223
Glassy carbon electrode modified by microcrystals of fullerene‐C60 mediates the voltammetric determination of uric acid (UA) in the presence of ascorbic acid (AA). Interference of AA was overcome owing to the ability of pretreated fullerene‐C60‐modified glassy carbon electrode. Based on its strong catalytic function towards the oxidation of UA and AA, the overlapping voltammetric response of uric acid and ascorbic acid is resolved into two well‐defined voltammetric peaks with lowered oxidation potential and enhanced oxidation currents under conditions of both linear sweep voltammetry (LSV) and Osteryoung square‐wave voltammetry (OSWV). At pH 7.2, a linear calibration graph is obtained for UA in linear sweep voltammetry over the range from 0.5 μM to 700 μM with a correlation coefficient of 0.9904 and a sensitivity of 0.0215 μA μM?1 . The detection limit (3σ) is 0.2 μM for standard solution. AA in less than four fold excess does not interfere. The sensitivity and detection limit in OSWV were found as 0.0255 μA μM?1 and 0.12 μM, for standard solution respectively. The presence of physiologically common interferents (i.e. adenine, hypoxanthine and xanthine) negligibly affects the response of UA. The fullerene‐C60‐modified electrode exhibited a stable, selective and sensitive response to uric acid in the presence of interferents. 相似文献
14.
Michael Quinones Yazhou Zhang Penelope Riascos Huey‐Min Hwang Winfred G. Aker Xiaojia He Ruomei Gao 《Photochemistry and photobiology》2014,90(2):374-379
Many biomolecules contain photoactive reducing agents, such as reduced nicotinamide adenine dinucleotide (NADH) and 6‐thioguanine (6‐TG) incorporated into DNA through drug metabolism. These reducing agents may produce reactive oxygen species under UVA irradiation or act as electron donors in various media. The interactions of C60 fullerenes with biological reductants and light energy, especially via the Type‐I electron‐transfer mechanism, are not fully understood although these factors are often involved in toxicity assessments. The two reductants employed in this work were NADH for aqueous solutions and 6‐TG for organic solvents. Using steady‐state photolysis and electrochemical techniques, we showed that under visible light irradiation, the presence of reducing agents enhanced C60‐mediated Type‐I reactions that generate superoxide anion (O2.?) at the expense of singlet oxygen (1O2) production. The quantum yield of O2.? production upon visible light irradiation of C60 is estimated below 0.2 in dipolar aprotic media, indicating that the majority of triplet C60 deactivate via Type‐II pathway. Upon UVA irradiation, however, both C60 and NADH undergo photochemical reactions to produce O2.?, which could lead to a possible synergistic toxicity effects. C60 photosensitization via Type‐I pathway is not observed in the absence of reducing agents. 相似文献
15.
Fullerence C60‐cryptand 22 was prepared and successfully applied as the electric carrier in the PVC electrode membrane of a bifunctional ion‐selective electrode for cations, e.g., Ag+ ions as well as anions, e.g., I? ions. The bifunctional ion‐selective electrode based on C60‐cryptand 22 can be applied as a Silver (Ag+) ion selective electrode with an internal electrode solution of 10?3 M AgNO3 in water (pH = 6.3), or as an Iodide (I?) ion selective electrode with an acidic internal electrode solution of 10?4 M KI(aq) (pH = 2) in which the cryptand 22 is protonated, and the C60‐cryptand 22 is changed to C60‐Cryptand22–H+ and becomes an anionic electro‐carrier to absorb the I? ion. The Ag+ ion selective electrode based on C60‐cryptand 22 gave a linear response with a near‐Nernstian slope (59.5 mV decade?1) within the concentration range 10?1‐10?3 M Ag+(aq). The Ag+ ion electrode exhibited comparatively good selectivity for silver ions, over other transition‐metal ions, alkali and alkaline earth metal ions. The Ag+ ion selective electrode with good stability and reproducibility was successfully used for the titration of Ag+(aq) with Cl? ions. The Iodide (I?) Ion selective electrode based on protonated C60–cryptand22‐H+ also showed a linear response with a nearly Nernstian slope (58.5 mV decade?1) within 10?1 ‐ 10?3 M I? (aq) and exhibited good selectivity for I? ions and had small selectivity coefficients (10?2–10?3) for most of other anions, e.g., F? , OH?, CH3COO?, SO42?, CO32?, CrO42?, Cr2O72? and PO43? ions. 相似文献
16.
Preparation of (C6F5)2SF+MF6? (M ? As, Sb) and Crystal Structure of (C6F5)2SF+SbF6? XeF+MF6? (M ? As, Sb) reacts with (C6F5)2S in HF to form (C6F5)2SF+MF6?. The deeply violet sulfonium salts can be kept without decomposition up to 24 h at room temperature. The hexafluoroantimonate salt crystallizes in the monoclinic space group P21/n with a = 1056.4(7) pm, b = 1446.3(10) pm, c = 1102.9(8) pm, β = 91.29(6)° und Z = 4. The SF-bond distance with 158.4(3) pm is of unusual length. Cations and anions are connected via interionic fluorine contacts to an infinite chain, in which cations and anions form to ABAB sequence along the chain. 相似文献
17.
Ultrafast Photoinduced Charge Separation Leading to High‐Energy Radical Ion‐Pairs in Directly Linked Corrole–C60 and Triphenylamine–Corrole‐C60 Donor–Acceptor Conjugates
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Dr. Kolanu Sudhakar Dr. Sabapathi Gokulnath Dr. Lingamallu Giribabu Gary N. Lim Tạ Trâm Prof. Dr. Francis D'Souza 《化学:亚洲杂志》2015,10(12):2708-2719
Closely positioned donor–acceptor pairs facilitate electron‐ and energy‐transfer events, relevant to light energy conversion. Here, a triad system TPACor‐C60 , possessing a free‐base corrole as central unit that linked the energy donor triphenylamine ( TPA ) at the meso position and an electron acceptor fullerene (C60) at the β‐pyrrole position was newly synthesized, as were the component dyads TPA‐Cor and Cor‐C60 . Spectroscopic, electrochemical, and DFT studies confirmed the molecular integrity and existence of a moderate level of intramolecular interactions between the components. Steady‐state fluorescence studies showed efficient energy transfer from 1 TPA* to the corrole and subsequent electron transfer from 1corrole* to fullerene. Further studies involving femtosecond and nanosecond laser flash photolysis confirmed electron transfer to be the quenching mechanism of corrole emission, in which the electron‐transfer products, the corrole radical cation ( Cor?+ in Cor‐C60 and TPA‐Cor?+ in TPACor‐C60 ) and fullerene radical anion (C60??), could be spectrally characterized. Owing to the close proximity of the donor and acceptor entities in the dyad and triad, the rate of charge separation, kCS, was found to be about 1011 s?1, suggesting the occurrence of an ultrafast charge‐separation process. Interestingly, although an order of magnitude slower than kCS, the rate of charge recombination, kCR, was also found to be rapid (kCR≈1010 s?1), and both processes followed the solvent polarity trend DMF>benzonitrile>THF>toluene. The charge‐separated species relaxed directly to the ground state in polar solvents while in toluene, formation of 3corrole* was observed, thus implying that the energy of the charge‐separated state in a nonpolar solvent is higher than the energy of 3corrole* being about 1.52 eV. That is, ultrafast formation of a high‐energy charge‐separated state in toluene has been achieved in these closely spaced corrole–fullerene donor–acceptor conjugates. 相似文献
18.
Dmitri V. Konarev Aleksey V. Kuzmin Salavat S. Khasanov Alexander F. Shestakov Akihiro Otsuka Hideki Yamochi Hiroshi Kitagawa Rimma N. Lyubovskaya 《化学:亚洲杂志》2020,15(17):2689-2695
Two salts of the aromatic hydrocarbon decacyclene, {cryptand[2.2.2](Cs+)} (decacyclene.?) ( 1 ) and {Bu3MeP+}(decacyclene.?) ( 2 ), were obtained. In both salts, decacyclene.? radical anions formed channels occupied by cations. However, corrugated hexagonal decacyclene.? layers could be outlined in the crystal structure of 1 with several side‐by‐side C???C approaches. The decacyclene.? radical anions showed strong distortion in both salts, deviating from the C3 symmetry owing to the repulsion of closely arranged hydrogen atoms and the Jahn‐Teller effect. Radical anions showed intense unusually low energy absorption in the IR‐range, with maxima at 4800 and 6000 cm?1. According to the carculations, these bands can originate from the SOMO‐LUMO+1 and SOMO‐LUMO+2 transitions, respectively. Radical anions exhibited a S=1/2 spin state, with an effective magnetic moment of 1.72 μB at 300 K. The decacyclene.? spin antiferromagnetically coupled with a Weiss temperature of ?11 K. Spin ordering was not observed down to 1.9 K owing to spin frustration in the hexagonal decacyclene.? layers. 相似文献
19.
Orientational Preference of Long,Multicenter Bonds in Radical Anion Dimers: A Case Study of π‐[TCNB]22− and π‐[TCNP]22−
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Dr. Marçal Capdevila‐Cortada Prof. Joel S. Miller Prof. Juan J. Novoa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6420-6432
The similar shape and electronic structure of the radical anions of 1,2,4,5‐tetracyanopyrazine (TCNP) and 1,2,4,5‐tetracyanobenzene (TCNB) suggest a similar relative orientation for their long, multicenter carbon?carbon bond in π‐[TCNP]22? and in π‐[TCNB]22?, in good accord with the Maximin Principle predictions. Instead, the two known structures of π‐[TCNP]22? have a D2h(θ=0°) and a C2(θ=30°) orientation (θ being the dihedral angle that determines the rotation of one radical anion relative to the other along the axis that passes through center of the two six‐membered rings). The only known π‐[TCNB]22? structure has a C2(θ=60°) orientation. The origin of these preferences was investigated for both dimers by computing (at the RASPT2/RASSCF(30,28) level) the variation with θ of the interaction energy (Eint) and the variation of the Eint components. It was found that: 1) a long, multicenter bond exists for all orientations; 2) the Eint(θ) angular dependence is similar in both dimers; 3) for all orientations the electrostatic component dominates the value of Eint(θ), although the dispersion and bonding components also play a relevant role; and 4) the Maximin Principle curve reproduces well the shape of the Eint(θ) curve for isolated dimers, although none of them reproduce the experimental preferences. Only after the (radical anion).? ??? cation+ interactions are also included in the model aggregate are the experimental data reproduced computationally. 相似文献
20.
Rakesh Puttreddy J. Mikko Rautiainen Toni Mkel Kari Rissanen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(51):18783-18791
A study of the strong N?X????O?N+ (X=I, Br) halogen bonding interactions reports 2×27 donor×acceptor complexes of N‐halosaccharins and pyridine N‐oxides (PyNO). DFT calculations were used to investigate the X???O halogen bond (XB) interaction energies in 54 complexes. A simplified computationally fast electrostatic model was developed for predicting the X???O XBs. The XB interaction energies vary from ?47.5 to ?120.3 kJ mol?1; the strongest N?I????O?N+ XBs approaching those of 3‐center‐4‐electron [N?I?N]+ halogen‐bonded systems (ca. 160 kJ mol?1). 1H NMR association constants (KXB) determined in CDCl3 and [D6]acetone vary from 2.0×100 to >108 m ?1 and correlate well with the calculated donor×acceptor complexation enthalpies found between ?38.4 and ?77.5 kJ mol?1. In X‐ray crystal structures, the N‐iodosaccharin‐PyNO complexes manifest short interaction ratios (RXB) between 0.65–0.67 for the N?I????O?N+ halogen bond. 相似文献