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1.
Alice E. Dearle Daniel J. Cutler Hector W. L. Fraser Sergio Sanz Edward Lee Sourav Dey Ismael F. Diaz‐Ortega Gary S. Nichol Hiroyuki Nojiri Marco Evangelisti Gopalan Rajaraman Jürgen Schnack Leroy Cronin Euan K. Brechin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(47):17059-17062
The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe34] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral FeIII ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.4 K and fields up to 35 T, reveal competing antiferromagnetic exchange interactions; DFT calculations showing that the magnitudes of the coupling constants are highly dependent on both the Fe‐O‐Fe angles and Fe?O distances. The simplicity of the synthetic methodology, and the structural similarity between [Fe34], bulk iron oxides, previous FeIII–oxo cages, and polyoxometalates (POMs), hints that much larger molecular FeIII oxides can be made. 相似文献
2.
Yaokang Lv Dr. Jun Cheng Dr. Alexander Steiner Prof. Lihua Gan Prof. Dominic S. Wright 《Angewandte Chemie (International ed. in English)》2014,53(7):1934-1938
Metal‐doped polyoxotitanium cages are a developing class of inorganic compounds which can be regarded as nano‐ and sub‐nano sized molecular relatives of metal‐doped titania nanoparticles. These species can serve as models for the ways in which dopant metal ions can be incorporated into metal‐doped titania (TiO2), a technologically important class of photocatalytic materials with broad applications in devices and pollution control. In this study a series of cobalt(II)‐containing cages in the size range ca. 0.7–1.3 nm have been synthesized and structurally characterized, allowing a coherent study of the factors affecting the band gaps in well‐defined metal‐doped model systems. Band structure calculations are consistent with experimental UV/Vis measurements of the TixOy absorption edges in these species and reveal that molecular dipole moment can have a profound effect on the band gap. The observation of a dipole‐induced band‐gap decrease mechanism provides a potentially general design strategy for the formation of low band‐gap inorganic cages. 相似文献
3.
Two LnIII ions are sandwiched by dinuclear CoII building blocks derived from a tris‐triazamacrocyclic ligand bearing pendant carboxylic acid functionality, 1,3,5‐tris((4,7‐bis(2‐carboxyethyl)‐1,4,7‐triazacyclonon‐1‐yl)methyl)‐benzene (H6L), giving rising to two nanoscale heterometallic metal–organic cages formulated as [Co4Ln2(LH2.5)2(H2O)4]·(ClO4)6·NO3·nH2O [Ln = Dy, n = 12 ( 1 ); Ln = Yb, n = 9 ( 2 )], whose internal cavity accommodates a guest NO3? anion. Their hexanuclear cage‐like architectures are maintained both in solution and solid states as confirmed by mass spectrum as well as X‐ray diffraction experiments. These two cages display ligand‐based fluorescence emissions and therefore both were chosen to be operated as fluorescent chemosensors for the detection of nitroaromatic compounds. Attractively, these metal–organic cages allow highly selective and sensitive detection of picric acid (PA) over other nitroaromatics in solution and suspension, and the fluorescence resonance energy transfer (FRET) between the cage probes and PA is mainly responsible for the remarkable detection efficiency. 相似文献
4.
Cu4P4X4Fe2 (X = Cl, Br) cages are formed upon reactions of octaethyl‐1,1′‐diphosphaferrocene (odpf) with the respective CuI halide in CH2Cl2/CH3CN solvent mixtures. These cages have adamantoid Cu4X4P2 cores with two planar anelated CuP2Fe rings as the flaps. Both complexes 1 and 2 feature tri‐ and tetracoordinate CuI ions and an additional acetonitrile solvent molecule in the crystal. In 1 , the solvent molecule is coordinated to one copper ion whereas it remains uncoordinated in 2 . The tricoordinate CuI ions show a slight pyramidalization at the metal atom and somewhat short contacts to the other tricoordinate CuI ion in 2 or the Cu3‐triangle in 1 . NMR spectroscopy revealed easy decoordination of the acetonitrile ligand from 1 and a dynamic “windshield‐wiper”‐type process that interconverts the differently coordinated phospholide rings of each odpf ligand and the tri‐ and tetracoordinate CuI ions. 相似文献
5.
A Porous Zirconium‐Based Metal‐Organic Framework with the Potential for the Separation of Butene Isomers
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Huimin Liu Prof. Dr. Yabing He Jingjing Jiao Dongjie Bai Dr. De‐li Chen Prof. Dr. Rajamani Krishna Prof. Dr. Banglin Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):14988-14997
By using a novel C3‐symmetrical tricarboxylate (4,4′,4′′‐benzene‐1,3,5‐triyl‐1,1′,1′′‐trinaphthoic acid), a novel zirconium‐based metal‐organic framework ZJNU‐30 was solvothermally synthesized and structurally characterized. Single‐crystal X‐ray structural analyses show that ZJNU‐30 consists of Zr6‐based nodes connected by the organic linkers to form a (3,8)‐connected network featuring the coexistence of two different polyhedral cages: octahedral and cuboctahedral cages with the dimensions of about 14 and 22 Å, respectively. Remarkably, ZJNU‐30 is very stable when exposed to air for one month. More importantly, with a moderately high surface area, hierarchical pore structures, and an aromatic‐rich pore surface in the framework, ZJNU‐30 , after activation, exhibits a promising potential for the selective adsorptive separation of industrially important butene isomers consisting of cis‐2‐butene, trans‐2‐butene, 1‐butene, and iso‐butene at ambient temperature. This separation was established exclusively by gas adsorption isotherms and simulated breakthrough experiments. To the best of our knowledge, this is the first study investigating porous metal‐organic frameworks for butene‐isomer separation. 相似文献
6.
The crystal and molecular structures of a series of structurally related 1,2,3‐triazole‐4,5‐dicarboxylate (LHtzdc = 1,2,3‐triazole‐4,5‐dicarboxylate) ligands for second metal ions were established via single‐crystal X‐ray structural analysis. [Cu (en)]2+ (en = ethylenediamine) was selected as a second metal ion, the two spare sites of the O atom from LHtzdc are coordinated to a single [Cu (en)]2+, and the [Cu (en)]2+ metal centres act as two outer pockets, which is an effective and innovative method of controlling the assembly of heterometallic cages. 相似文献
7.
M. Paula C. Campello Dr. Sara Lacerda Dr. Isabel C. Santos Dr. Giovannia A. Pereira Dr. Carlos F. G. C. Geraldes Prof. Dr. Jan Kotek Dr. Petr Hermann Dr. Jakub Vaněk Přemysl Lubal Vojtěch Kubíček Dr. Éva Tóth Isabel Santos Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(28):8446-8465
Complexes of 4,10‐bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H6do2a2p, H6 L ) with transition metal and lanthanide(III) ions were investigated. The stability constant values of the divalent and trivalent metal‐ion complexes are between the corresponding values of H4dota and H8dotp complexes, as a consequence of the ligand basicity. The solid‐state structures of the ligand and of nine lanthanide(III) complexes were determined by X‐ray diffraction. All the complexes are present as twisted‐square‐antiprismatic isomers and their structures can be divided into two series. The first one involves nona‐coordinated complexes of the large lanthanide(III) ions (Ce, Nd, Sm) with a coordinated water molecule. In the series of Sm, Eu, Tb, Dy, Er, Yb, the complexes are octa‐coordinated only by the ligand donor atoms and their coordination cages are more irregular. The formation kinetics and the acid‐assisted dissociation of several LnIII–H6 L complexes were investigated at different temperatures and compared with analogous data for complexes of other dota‐like ligands. The [Ce( L )(H2O)]3? complex is the most kinetically inert among complexes of the investigated lanthanide(III) ions (Ce, Eu, Gd, Yb). Among mixed phosphonate–acetate dota analogues, kinetic inertness of the cerium(III) complexes is increased with a higher number of phosphonate arms in the ligand, whereas the opposite is true for europium(III) complexes. According to the 1H NMR spectroscopic pseudo‐contact shifts for the Ce–Eu and Tb–Yb series, the solution structures of the complexes reflect the structures of the [Ce(H L )(H2O)]2? and [Yb(H L )]2? anions, respectively, found in the solid state. However, these solution NMR spectroscopic studies showed that there is no unambiguous relation between 31P/1H lanthanide‐induced shift (LIS) values and coordination of water in the complexes; the values rather express a relative position of the central ions between the N4 and O4 planes. 相似文献
8.
Ping Peng Fang‐Fang Li Venkata S. Pavan K. Neti Alejandro J. Metta‐Magana Luis Echegoyen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(1):164-167
Given the unique structural and electronic properties of C60, metal–organic frameworks (MOFs) containing C60 linkers are expected to exhibit interesting characteristics. A new hexakisfullerene derivative possessing two pairs of phenyl pyridine groups attached to two methano‐carbon atoms located at the trans‐1 positions was designed and synthesized. The four pyridyl nitrogen atoms define a perfectly planar rectangle. This new C60 derivative was used to assemble the first fullerene‐linked two‐dimensional MOF by coordination with Cd2+. 相似文献
9.
Design,Synthesis, and X‐Ray Crystal Structure of a Fullerene‐Linked Metal–Organic Framework
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Dr. Ping Peng Dr. Fang‐Fang Li Venkata S. Pavan K. Neti Dr. Alejandro J. Metta‐Magana Prof. Dr. Luis Echegoyen 《Angewandte Chemie (International ed. in English)》2014,53(1):160-163
Given the unique structural and electronic properties of C60, metal–organic frameworks (MOFs) containing C60 linkers are expected to exhibit interesting characteristics. A new hexakisfullerene derivative possessing two pairs of phenyl pyridine groups attached to two methano‐carbon atoms located at the trans‐1 positions was designed and synthesized. The four pyridyl nitrogen atoms define a perfectly planar rectangle. This new C60 derivative was used to assemble the first fullerene‐linked two‐dimensional MOF by coordination with Cd2+. 相似文献
10.
Durgesh V. Wagle Steven P. Kelley Gary A. Baker Kanishka Sikligar Jerry L. Atwood 《Angewandte Chemie (International ed. in English)》2020,59(21):8062-8065
A hexameric metal–organic nanocapsule is assembled from pyrogallol[4]arene units, which are stitched together with indium ions. This indium‐seamed capsule is the first instance of a M24L6 type hexameric coordination cage held together exclusively by trivalent metal ions. Explicitly, unlike previously reported pyrogallol[4]arene‐based metal‐seamed capsules, the current In3+ seamed capsule is entirely supported by O→In coordinate bonds. This work demonstrates the important proof of concept of the ability of pyrogallol[4]arene to react with metals in higher oxidation states to assemble into atomically‐precise hexameric coordination cages. As such, these results open up exciting avenues toward the assembly of previously unanticipated metal–organic capsules, for example offering inspiration for tackling metals exhibiting high valence states such as in the lanthanide and actinide series. 相似文献
11.
Aleksandar R. Todorov Dr. Martin Nieger Dr. Juho Helaja 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(23):7269-7277
Novel 4‐hydroxyquinoline (4HQ) based tautomeric switches are reported. 4HQs equipped with coordinative side arms (8‐arylimino and 3‐piperidin‐1‐ylmethyl groups) were synthesized to access O‐ or N‐selective chelation of Zn2+ and Cd2+ ions by 4HQ. In the case of the monodentate arylimino group, O chelation of metal ions induces concomitant switching of phenol tautomer to the keto form in nonpolar or aprotic media. This change is accompanied by selective and highly sensitive fluorometric sensing of Zn2+ ions. In the case of the bidentate 8‐(quinolin‐8‐ylimino)methyl side arm, NMR studies in CD3OD indicated that both Cd2+ and Zn2+ ions afford N chelation for 4HQ, coexisting with tautomeric switching from quinolin‐4(1H)‐one to quinolin‐4‐olate. In corroboration, UV/Vis‐monitored metal‐ion titrations in toluene and methanol implied similar structural changes. Additionally, fluorescence measurements indicated that the metal‐triggered tautomeric switching is associated with compound signaling properties. The results are supported by DFT calculations at the B3LYP 6‐31G* level. Several X‐ray structures of metal‐free and metal‐chelating 4HQ are presented to support the solution studies. 相似文献
12.
Kristof Seubert Dominik Böhme Jutta Kösters Wei‐Zheng Shen Eva Freisinger Prof. Dr. Jens Müller 《无机化学与普通化学杂志》2012,638(11):1761-1767
Metal‐mediated base pairs can be used to insert metal ions into nucleic acids at precisely defined positions. As structural data on the resulting metal‐modified DNA are scarce, appropriate model complexes need to be synthesized and structurally characterized. Accordingly, the molecular structures of nine transition metal complexes of N‐methyl‐2, 2'‐dipicolylamine (dipic) are reported. In combination with an azole‐containing artificial nucleoside, this tridentate ligand had recently been used to generate metal‐mediated base pairs (Chem. Commun. 2011 , 47, 11041–11043). The PdII and PtII complexes reported here confirm that the formation of planar complexes (as required for a metal‐mediated base pair) comprising N‐methyl‐2, 2'‐dipicolylamine is possible. Two HgII complexes with differing stoichiometry indicate that a planar structure might also be formed with this metal ion, even though it is not favored. In the complex [Ag2(dipic)2](ClO4)2, the two AgI ions are located close to one another with an Ag ··· Ag distance of 2.9152(3) Å, suggesting the presence of a strong argentophilic interaction. 相似文献
13.
Beyond Molecules: Mesoporous Supramolecular Frameworks Self‐Assembled from Coordination Cages and Inorganic Anions
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Dong Luo Prof. Dr. Xiao‐Ping Zhou Prof. Dr. Dan Li 《Angewandte Chemie (International ed. in English)》2015,54(21):6190-6195
Biological function arises by the assembly of individual biomolecular modules into large aggregations or highly complex architectures. A similar strategy is adopted in supramolecular chemistry to assemble complex and highly ordered structures with advanced functions from simple components. Here we report a series of diamond‐like supramolecular frameworks featuring mesoporous cavities, which are assembled from metal‐imidazolate coordination cages and various anions. Small components (metal ions, amines, aldehydes, and anions) are assembled into the hierarchical complex structures through multiple interactions including covalent bonds, dative bonds, and weak C? H???X (X=O, F, and π) hydrogen bonds. The mesoporous cavities are large enough to trap organic dye molecules, coordination cages, and vitamin B12. The study is expected to inspire new types of crystalline supramolecular framework materials based on coordination motifs and inorganic ions. 相似文献
14.
Fokko M. Mulder Dr. Marnix Wagemaker Dr. Lambert van Eijck Dr. Gordon J. Kearley Prof. Dr. 《Chemphyschem》2008,9(9):1331-1337
The lack of practical methods for hydrogen storage is still a major bottleneck in the realization of an energy economy based on hydrogen as energy carrier. 1 Storage within solid‐state clathrate hydrates, 2 – 4 and in the clathrate hydrate of tetrahydrofuran (THF), has been recently reported. 5 , 6 In the latter case, stabilization by THF is claimed to reduce the operation pressure by several orders of magnitude close to room temperature. Here, we apply in situ neutron diffraction to show that—in contrast to previous reports[5, 6]—hydrogen (deuterium) occupies the small cages of the clathrate hydrate only to 30 % (at 274 K and 90.5 bar). Such a D2 load is equivalent to 0.27 wt. % of stored H2. In addition, we show that a surplus of D2O results in the formation of additional D2O ice Ih instead of in the production of sub‐stoichiometric clathrate that is stabilized by loaded hydrogen (as was reported in ref. 6 ). Structure‐refinement studies show that [D8]THF is dynamically disordered, while it fills each of the large cages of [D8]THF?17D2O stoichiometrically. Our results show that the clathrate hydrate takes up hydrogen rapidly at pressures between 60 and 90 bar (at about 270 K). At temperatures above ≈220 K, the H‐storage characteristics of the clathrate hydrate have similarities with those of surface‐adsorption materials, such as nanoporous zeolites and metal–organic frameworks, 7 , 8 but at lower temperatures, the adsorption rates slow down because of reduced D2 diffusion between the small cages. 相似文献
15.
Chaowei Hao Ying Zhao Yong Zhou Lijuan Zhou Yizhuang Xu Dujin Wang Duanfu Xu 《Journal of Polymer Science.Polymer Physics》2007,45(13):1589-1598
The rheological behavior of poly(vinyl pyrrolidone) (PVP)/N,N‐dimethylformamide (DMF) solutions containing metal chlorides (LiCl, CaCl2, and CoCl2) were investigated, and the results showed that the nature of the metal ions and their concentration had an obvious effect on the steady‐state rheological behavior of PVP–DMF solutions with different molecular weights. The apparent viscosity of the PVP–DMF solutions increased with an increasing metal‐ion concentration, and the viscosity increment was dependent on the metal‐ion variety. For a CaCl2‐containing PVP–DMF solution, for example, the critical shear rate at the onset of shear thinning became smaller with increasing CaCl2 concentration. It was believed that multiple interactions among metal ions, carbonyl groups of PVP, and amide groups in DMF determined the solution properties of these complex fluids; therefore, 13C NMR spectroscopy was used to detect the interactions in systems of PVP–CaCl2–DMF and PVP–LiCl–DMF solutions. NMR data showed that there were obvious interactions between the metal ions and the carbonyl groups of the PVP segments in the DMF solutions. Furthermore, IR spectra of the PVP/metal chloride composites demonstrated that the interaction between the metal ions and carbonyl groups in the PVP unit occurred and that the PVP chain underwent conformational variations with the metal‐ion concentration. DSC results indicated that the glass transition temperatures of the PVP/metal chloride composites increased with the addition of metal ions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1589–1598, 2007 相似文献
16.
Marina Frank Dr. Mark D. Johnstone Prof. Dr. Guido H. Clever 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14104-14125
This Review covers design strategies, synthetic challenges, host–guest chemistry, and functional properties of interlocked supramolecular cages. Some dynamic covalent organic structures are discussed, as are selected examples of interpenetration in metal–organic frameworks, but the main focus is on discrete coordination architectures, that is, metal‐mediated dimers. Factors leading to interpenetration, such as geometry, flexibility and chemical makeup of the ligands, coordination environment, solvent effects, and selection of suitable counter anions and guest molecules, are discussed. In particular, banana‐shaped bis‐pyridyl ligands together with square‐planar metal cations have proven to be suitable building blocks for the construction of interpenetrated double‐cages obeying the formula [M4L8]. The peculiar topology of these double‐cages results in a linear arrangement of three mechanically coupled pockets. This allows for the implementation of interesting guest encapsulation effects such as allosteric binding and template‐controlled selectivity. In stimuli‐responsive systems, anionic triggers can toggle the binding of neutral guests or even induce complete structural conversions. The increasing structural and functional complexity in this class of self‐assembled hosts promises the construction of intelligent receptors, novel catalytic systems, and functional materials. 相似文献
17.
Organization and Energy Transfer of Fused Aromatic Hydrocarbon Guests within Anion‐Confining Nanochannel MOFs
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Dr. Tae Hwan Noh Haeri Lee Jaeseong Jang Prof. Dr. Ok‐Sang Jung 《Angewandte Chemie (International ed. in English)》2015,54(32):9284-9288
The self‐assembly of ZnII ions with 1,3,5‐tris(isonicotinoyloxyethyl)cyanurate produces new topological (42?124)3(43)4 2D metal–organic frameworks (MOFs) with anion‐confining cages. The eclipsed assembly of each 2D MOF by π–π stacking of cyanurate moieties (3.352(5) Å) forms 3D MOFs consisting of nanochannels (10.5 Å). Two of the three anions are confined in each peanut‐type cage, resulting in hydrophobicity of the nanochannels. The hydrophobic nanochannel effectively adsorbs a wide range of fused aromatic hydrocarbons (FAHs) as monomers or dimers, rendering it potentially highly useful as an energy‐transfer material. 相似文献
18.
Reducing Capsule Based on Electron Programming: Versatile Synthesizer for Size‐Controlled Ultra‐Small Metal Clusters
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Dr. Tetsuya Kambe Dr. Takane Imaoka Prof. Kimihisa Yamamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16406-16409
Controlled reducing capsules with a specific number of reducing electrons were achieved by appropriately placed BH3 units in the dendritic polyphenylazomethines (DPAs). Using the 1:1 coordination fashion on their basic branches with radius affinity gradient, the 4th generation DPA (DPAG4) possessing four BH3 units in the central positions was prepared as a template synthesizer for size‐controlled ultra‐small metal clusters. This was well‐demonstrated by reduction of Ag, Pt, and other metal ions resulting in monodispersed ultra‐small clusters. 相似文献
19.
Single Crystal‐to‐Single Crystal Site‐Selective Postsynthetic Metal Exchange in a Zn–MOF Based on Semi‐Rigid Tricarboxylic Acid and Access to Bimetallic MOFs
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Dr. Alankriti Bajpai Pujari Chandrasekhar Dr. Savitha Govardhan Dr. Rahul Banerjee Prof. Dr. Jarugu Narasimha Moorthy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2759-2765
The metal ions in a neutral Zn–MOF constructed from tritopic triacid H3L with inherent concave features, rigid core, and peripheral flexibility are found to exist in two distinct SBUs, that is, 0D and 1D. This has allowed site‐selective postsynthetic metal exchange (PSME) to be investigated and reactivities of the metal ions in two different environments in coordination polymers to be contrasted for the first time. Site‐selective transmetalation of Zn ions in the discrete environment is shown to occur in a single crystal‐to‐single crystal (SCSC) fashion, with metal ions such as Fe3+, Ru3+, Cu2+, Co2+, etc., whereas those that are part of 1D SBU sustain structural integrity, leading to novel bimetallic MOFs, which are inaccessible by conventional approaches. To the best of our knowledge, site‐selective postsynthetic exchange of an intraframework metal ion in a MOF that contains metal ions in discrete as well as polymeric SBUs is heretofore unprecedented. 相似文献
20.
Bandgap Engineering of Titanium–Oxo Clusters: Labile Surface Sites Used for Ligand Substitution and Metal Incorporation
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Jin‐Xiu Liu Mei‐Yan Gao Dr. Wei‐Hui Fang Prof. Dr. Lei Zhang Prof. Dr. Jian Zhang 《Angewandte Chemie (International ed. in English)》2016,55(17):5160-5165
Through the labile coordination sites of a robust phosphonate‐stabilized titanium–oxo cluster, 14 O‐donor ligands have been successfully introduced without changing the cluster core. The increasing electron‐withdrawing effect of the organic species allows the gradual reduction of the bandgaps of the {Ti6} complexes. Transition‐metal ions are then incorporated by the use of bifunctional O/N‐donor ligands, organizing these {Ti6} clusters into polymeric structures. The coordination environments of the applied metal ions show significant influence on their visible‐light adsorption. Both the above structural functionalizations also tune the photocatalytic H2 production activities of these clusters. This work provides a systematic bandgap engineering study of titanium–oxo clusters, which is important not only for their future photocatalytic applications, also for the better understanding of the structure–property relationships. 相似文献