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1.
New Trifluoromethylated Derivatives of Metal Nitride Clusterfullerenes: Sc3N@Ih‐C80(CF3)14 and Sc3N@D5h‐C80(CF3)16
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Tao Wei Dr. Nadezhda B. Tamm Prof. Dr. Shangfeng Yang Prof. Dr. Sergey I. Troyanov 《化学:亚洲杂志》2014,9(9):2449-2452
Trifluoromethylated derivatives of Sc3N@Ih‐C80 and Sc3N@D5h‐C80 were synthesized by the reaction with CF3I at 440 °C. HPLC separation of the mixture of Sc3N@D5h‐C80(CF3)n derivatives resulted in isolation and X‐ray structure determination of Sc3N@D5h‐C80(CF3)16, which represents a precursor of the known Sc3N@D5h‐C80(CF3)18. Among the CF3 derivatives of Sc3N@Ih‐C80, two new isomers of Sc3N@Ih‐C80(CF3)14 ( Sc‐14‐VI and Sc‐14‐VII ) were isolated by HPLC, and their molecular structures were determined by X‐ray diffraction, thus enabling a comprehensive comparison of altogether seven isomers. Two types of addition patterns with different orientations of the Sc3N cluster relative to the Ih‐C80 fullerene cage were established. In particular, Sc‐14‐VII represents a direct precursor of the known Sc3N@Ih‐C80(CF3)16‐ II . All molecular structures exhibit an ordered position of a Sc3N cluster inside the fullerene C80 cage. 相似文献
2.
Synthesis,Isolation and Structure of Trifluoromethylated Fullerene D3‐C78, C78(1)(CF3)10−18
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Maria P. Kosaya Dr. Maria A. Fritz Victor A. Brotsman Dr. Nadezhda B. Tamm Dr. Daria V. Ignat'eva Prof. Dr. Sergey I. Troyanov 《化学:亚洲杂志》2016,11(7):1000-1003
High‐temperature trifluoromethylation of fullerene C78 followed by HPLC separation of C78(CF3)n derivatives resulted in the isolation and X‐ray structural characterization of 15 compounds, that is, two C78(1)(CF3)10, three C78(1)(CF3)12, four C78(1)(CF3)14, and five C78(1)(CF3)16 isomers as well as one isomer of C78(1)(CF3)18. The addition patterns of the C78(1)(CF3)n molecules are discussed in terms of trifluoromethylation pathways and relative formation energies. 相似文献
3.
Synthesis,Isolation and Structures of Trifluoromethylated Fullerenes D2‐C76, C76(1)(CF3)10–18
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《化学:亚洲杂志》2018,13(16):2027-2030
High‐temperature trifluoromethylation of fullerene C76 chlorination products followed by HPLC separation of C76(CF3)n derivatives resulted in the isolation and X‐ray structural characterization of thirteen C76(1)(CF3)n compounds including nine new isomers such as one isomer of C76(1)(CF3)10, two C76(1)(CF3)12, three C76(1)(CF3)14, one C76(1)(CF3)16, and two isomers of C76(1)(CF3)18. Depending on their addition patterns, C76(1)(CF3)n isomers are divided into three subgroups and discussed in terms of trifluoromethylation pathways and relative formation energies. 相似文献
4.
Blending Non‐Group‐3 Transition Metal and Rare‐Earth Metal into a C80 Fullerene Cage with D5h Symmetry
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Dr. Tao Wei Fei Jin Runnan Guan Prof. Dr. Jing Huang Dr. Muqing Chen Prof. Dr. Qunxiang Li Prof. Dr. Shangfeng Yang 《Angewandte Chemie (International ed. in English)》2018,57(32):10273-10277
Rare‐earth metals have been mostly entrapped into fullerene cages to form endohedral clusterfullerenes, whereas non‐Group‐3 transition metals that can form clusterfullerenes are limited to titanium (Ti) and vanadium (V), and both are exclusively entrapped within an Ih‐C80 cage. Non‐Group‐3 transition‐metal‐containing endohedral fullerenes based on a C80 cage with D5h symmetry, VxSc3?xN@D5h‐C80 (x=1, 2), have now been synthesized, which exhibit two variable cluster compositions. The molecular structure of VSc2N@D5h‐C80 was unambiguously determined by X‐ray crystallography. According to a comparative study with the reported Ti‐ and V‐containing clusterfullerenes based on a Ih‐C80 cage and the analogous D5h‐C80‐based metal nitride clusterfullerenes containing rare‐earth metals only, the decisive role of the non‐Group‐3 transition metal on the formation of the corresponding D5h‐C80‐based clusterfullerenes is unraveled. 相似文献
5.
Nadezhda B. Tamm Runnan Guan Shangfeng Yang Erhard Kemnitz Sergey I. Troyanov 《化学:亚洲杂志》2019,14(12):2108-2111
High‐temperature trifluoromethylation of isolated‐pentagon‐rule (IPR) fullerene C92 chlorination products followed by HPLC separation of C92(CF3)n derivatives resulted in the isolation and X‐ray structural characterization of IPR C92(38)(CF3)18 and non‐classical C92(NC)(CF3)22. The formation of C92(38)(CF3)18 as the highest CF3 derivative of the known isomer C92(38) can be expected. The formation of C92(NC)(CF3)22 was interpreted as chlorination‐promoted cage transformation of C92(38) followed by trifluoromethylation of non‐classical C92(NC) chloride. Noticeably, C92(NC)(CF3)22 shows the highest degree of trifluoromethylation among all known CF3 derivatives of fullerenes. The addition patterns of C92(38)(CF3)18 and C92(NC)(CF3)22 are discussed and compared to the chlorination patterns of C92(38)Cln compounds. 相似文献
6.
Capturing C90 Isomers as CF3 Derivatives: C90(30)(CF3)14, C90(35)(CF3)16/18, and C90(45)(CF3)16/18
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High‐temperature trifluoromethylation of a C90 isomeric mixture with CF3I followed by HPLC separation of C90(CF3)n isomers resulted in the isolation of several individual C90(CF3)14?18 compounds. Single crystal X‐ray diffraction with the use of synchrotron radiation resulted in the structure determination of C90(30)(CF3)14, C90(35)(CF3)16/18, and C90(45)(CF3)16/18. Their addition patterns are discussed and compared with the known isomers C90(30)(CF3)18 and C90(35)(CF3)14, respectively. The presence of the most stable C90 isomer, C90(45), in the fullerene soot has been confirmed for the first time. 相似文献
7.
Natalia A. Romanova Maria A. Fritz Dr. Kaichin Chang Dr. Nadezhda B. Tamm Dr. Alexey A. Goryunkov Prof. Lev N. Sidorov Dr. Chuanbao Chen Prof. Shangfeng Yang Prof. Erhard Kemnitz Prof. Sergey I. Troyanov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11707-11716
Trifluoromethylation of a higher fullerene mixture with CF3I was performed in ampoules at 550 °C. HPLC separation followed by crystal growth and X‐ray diffraction study resulted in the structure elucidation of nine CF3 derivatives of D2d‐C84 (isomer 23). The molecular structures of C84(23)(CF3)4, C84(23)(CF3)8, C84(23)(CF3)10, C84(23)(CF3)12, two isomers of C84(23)(CF3)14, two isomers of C84(23)(CF3)16, and C84(23)(CF3)18 were discussed in terms of their addition patterns and the relative formation energies. Extensive theoretical DFT calculations were performed to identify the most stable molecular structures. It was found that the addition of CF3 groups to the C84(23) fullerene is governed by two main rules: no additions in positions of triple hexagon junctions and predominantly para additions in C6(CF3)2 hexagons on the fullerene cage. The only exception with an isolated CF3 group in C84(23)(CF3)12 is discussed in more detail. 相似文献
8.
Kaichin Chang Maria A. Fritz Dr. Nadezhda B. Tamm Dr. Alexey A. Goryunkov Prof. Lev N. Sidorov Dr. Chuanbao Chen Prof. Shangfeng Yang Prof. Erhard Kemnitz Prof. Sergey I. Troyanov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):578-587
Trifluoromethylation of higher fullerene mixtures with CF3I was performed in ampoules at 400 to 420 and 550 to 560 °C. HPLC separation followed by crystal growth and X‐ray diffraction studies allowed the structure elucidation of nine CF3 derivatives of D2‐C84 (isomer 22). Molecular structures of two isomers of C84(22)(CF3)12, two isomers of C84(22)(CF3)14, four isomers of C84(22)(CF3)16, and one isomer of C84(22)(CF3)20 were discussed in terms of their addition patterns and relative formation energies. DFT calculations were also used to predict the most stable molecular structures of lower CF3 derivatives, C84(22)(CF3)2–10. It was found that the addition of CF3 groups to C84(22) is governed by two rules: additions can only occur at para positions of C6(CF3)2 hexagons and no additions can occur at triple‐hexagon‐junction positions on the fullerene cage. 相似文献
9.
Nataliya A. Samoylova Nikita M. Belov Victor A. Brotsman Dr. Ilya N. Ioffe Dr. Natalia S. Lukonina Dr. Vitaliy Yu. Markov Dr. Adrian Ruff Alexey V. Rybalchenko Paul Schuler Olesya O. Semivrazhskaya Prof. Dr. Bernd Speiser Prof. Dr. Sergey I. Troyanov Prof. Dr. Tatiana V. Magdesieva Dr. Alexey A. Goryunkov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(52):17969-17979
Novel difluoromethylenated [70]fullerene derivatives, C70(CF2)n (n=1–3), were obtained by the reaction of C70 with sodium difluorochloroacetate. Two major products, isomeric C70(CF2) mono‐adducts with [6,6]‐open and [6,6]‐closed configurations, were isolated and their homofullerene and methanofullerene structures were reliably determined by a variety of methods that included X‐ray analysis and high‐level spectroscopic techniques. The [6,6]‐open isomer of C70(CF2) constitutes the first homofullerene example of a non‐hetero [70]fullerene derivative in which functionalisation involves the most reactive bond in the polar region of the cage. Voltammetric estimation of the electron affinity of the C70(CF2) isomers showed that it is substantially higher for the [6,6]‐open isomer (the 70‐electron π‐conjugated system is retained) than the [6,6]‐closed form, the latter being similar to the electron affinity of pristine C70. In situ ESR spectroelectrochemical investigation of the C70(CF2) radical anions and DFT calculations of the hyperfine coupling constants provide evidence for the first example of an inter‐conversion between the [6,6]‐closed and [6,6]‐open forms of a cage‐modified fullerene driven by an electrochemical one‐electron transfer. Thus, [6,6]‐closed C70(CF2) constitutes an interesting example of a redox‐switchable fullerene derivative. 相似文献
10.
High‐temperature chlorination of C90‐containing fullerene fraction resulted in the isolation and X‐ray structural characterization of C90(1)Cl10/12, the first derivatives of a relatively unstable isomer D5h‐C90(1) with a nanotubular shape. In the crystal structure, three isomers of both C90(1)Cl10 and C90(1)Cl12 with similar chlorination patterns co‐crystallize in the same crystallographic site. Thus, in contrast to the previous reports, D5h‐C90(1) is present, though with a low abundance, in the fullerene soot produced by arc‐discharge method with undoped graphite rods. 相似文献
11.
Lipiao Bao Ying Li Pengyuan Yu Wangqiang Shen Peng Jin Xing Lu 《Angewandte Chemie (International ed. in English)》2020,59(13):5259-5262
Encapsulating one to three metal atoms or a metallic cluster inside fullerene cages affords endohedral metallofullerenes (EMFs) classified as mono‐, di‐, tri‐, and cluster‐EMFs, respectively. Although the coexistence of various EMF species in soot is common for rare‐earth metals, we herein report that europium tends to prefer the formation of mono‐EMFs. Mass spectroscopy reveals that mono‐EMFs (Eu@C2n) prevail in the Eu‐containing soot. Theoretical calculations demonstrate that the encapsulation energy of the endohedral metal accounts for the selective formation of mono‐EMFs and rationalize similar observations for EMFs containing other metals like Ca, Sr, Ba, or Yb. Consistently, all isolated Eu‐EMFs are mono‐EMFs, including Eu@D3h(1)‐C74, Eu@C2v(19138)‐C76, Eu@C2v(3)‐C78, Eu@C2v(3)‐C80, and Eu@D3d(19)‐C84, which are identified by crystallography. Remarkably, Eu@C2v(19138)‐C76 represents the first Eu‐containing EMF with a cage that violates the isolated‐pentagon‐rule, and Eu@C2v(3)‐C78 is the first C78‐based EMF stabilized by merely one metal atom. 相似文献
12.
《Angewandte Chemie (International ed. in English)》2017,56(39):11990-11994
As an emerging member of endohedral fullerenes, metal cyanide clusterfullerenes (CYCF) are unique in terms of the encapsulation of a monometallic cluster. To date the reported carbon cages of CYCFs are limited to C82 and C76, and little is known about the chemical reactivity of CYCFs. Herein, two isomers of the first C84‐based CYCFs, YCN@C84, were isolated as trifluoromethyl derivatives, including YCN@C84(23)(CF3)18 and three isomers of YCN@C84(13)(CF3)16, which are based on a unique chiral C 2‐C84(13) cage. As a common feature of the CF3 addition patterns, the YCN@C84(CF3)16/18 compounds are stabilized by the formation of isolated C=C bonds and benzenoid rings on the carbon cages. The interplay between the endohedral YCN cluster and the exhohedral CF3 addends was unveiled according to single‐crystal X‐ray diffraction studies, thus offering new insight into the chemical reactivity of CYCFs. 相似文献
13.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(39):12152-12156
As an emerging member of endohedral fullerenes, metal cyanide clusterfullerenes (CYCF) are unique in terms of the encapsulation of a monometallic cluster. To date the reported carbon cages of CYCFs are limited to C82 and C76, and little is known about the chemical reactivity of CYCFs. Herein, two isomers of the first C84‐based CYCFs, YCN@C84, were isolated as trifluoromethyl derivatives, including YCN@C84(23)(CF3)18 and three isomers of YCN@C84(13)(CF3)16, which are based on a unique chiral C 2‐C84(13) cage. As a common feature of the CF3 addition patterns, the YCN@C84(CF3)16/18 compounds are stabilized by the formation of isolated C=C bonds and benzenoid rings on the carbon cages. The interplay between the endohedral YCN cluster and the exhohedral CF3 addends was unveiled according to single‐crystal X‐ray diffraction studies, thus offering new insight into the chemical reactivity of CYCFs. 相似文献
14.
Dr. Mitsuaki Suzuki Dr. Naomi Mizorogi Tao Yang Prof. Dr. Filip Uhlik Prof. Dr. Zdenek Slanina Prof. Dr. Xiang Zhao Prof. Dr. Michio Yamada Prof. Dr. Yutaka Maeda Prof. Dr. Tadashi Hasegawa Prof. Dr. Shigeru Nagase Prof. Dr. Xing Lu Prof. Dr. Takeshi Akasaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):17125-17130
Although all the pure‐carbon fullerene isomers above C60 reported to date comply with the isolated pentagon rule (IPR), non‐IPR structures, which are expected to have different properties from those of IPR species, are obtainable either by exohedral modification or by endohedral atom doping. This report describes the isolation and characterization of a new endohedral metallofullerene (EMF), La2@C76, which has a non‐IPR fullerene cage. The X‐ray crystallographic result for the La2@C76/[NiII(OEP)] (OEP=octaethylporphyrin) cocrystal unambiguously elucidated the Cs(17 490)‐C76 cage structure, which contains two adjacent pentagon pairs. Surprisingly, multiple metal sites were distinguished from the X‐ray data, which implies dynamic behavior for the two La3+ cations inside the cage. This dynamic behavior was also corroborated by variable‐temperature 139 La NMR spectroscopy. This phenomenon conflicts with the widely accepted idea that the metal cations in non‐IPR EMFs invariably coordinate strongly with the negatively charged fused‐pentagon carbons, thereby providing new insights into modern coordination chemistry. Furthermore, our electrochemical and computational studies reveal that La2@Cs(17 490)‐C76 has a larger HOMO–LUMO gap than other dilanthanum‐EMFs with IPR cage structures, such as La2@D3h(5)‐C78 and La2@Ih(7)‐C80, which implies that IPR is no longer a strict rule for EMFs. 相似文献
15.
Tyler T. Clikeman Dr. Igor V. Kuvychko Dr. Natalia B. Shustova Dr. Yu‐Sheng Chen Dr. Alexey A. Popov Dr. Olga V. Boltalina Prof. Steven H. Strauss 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(16):5070-5080
The sequential addition of CN? or CH3? and electrophiles to three perfluoroalkylfullerenes (PFAFs), Cs‐C70(CF3)8, C1‐C70(CF3)10, and Cs‐p‐C60(CF3)2, was carried out to determine the most reactive individual fullerene C atoms (as opposed to the most reactive C?C bonds, which has previously been studied). Each PFAF reacted with CH3? or CN? to generate metastable PFAF(CN)? or PFAF(CH3)22? species with high regioselectivity (i.e., one or two predominant isomers). They were treated with electrophiles E+ to generate PFAF(CN)(E) or PFAF(CH3)2(E)2 derivatives, also with high regioselectivity (E+=CN+, CH3+, or H+). All of the predominant products, characterized by mass spectrometry and 19F NMR spectroscopy, are new compounds. Some could be purified by HPLC to give single isomers. Two of them, C70(CF3)8(CN)2 and C70(CF3)10(CH3)2(CN)2, were characterized by single‐crystal X‐ray diffraction. DFT calculations were used to propose whether a particular reaction is under kinetic or thermodynamic control. 相似文献
16.
Victor A. Brotsman Viktor P. Bogdanov Alexey V. Rybalchenko Evgenia P. Galanicheva Nikita M. Belov Dr. Vitaliy Yu. Markov Dr. Natalia S. Lukonina Dr. Ilya N. Ioffe Prof. Dr. Sergey I. Troyanov Prof. Dr. Erhard Kemnitz Dr. Alexey A. Goryunkov 《化学:亚洲杂志》2016,11(13):1945-1954
CF3‐derivatized fullerenes prove once again to be promising scaffolds for regioselective fullerene functionalization: now with the smallest possible addends—hydrogen atoms. Hydrogenation of Cs‐C70(CF3)8 and C1‐C70(CF3)10 by means of reduction with Zn/Cu couple in the presence of water proceeds regioselectively, yielding only one major isomer of C70(CF3)8H2 and only two for C70(CF3)10H2, whose addition patterns are combined in the only abundant isomer of C70(CF3)10H4. The observed selectivity is governed by the electronic structure of trifluoromethylated substrates. Interestingly, we discovered that Clar's theory can be utilized to predict the regiochemistry of functionalization, and we look forward to testing it on forthcoming cases of derivatization of pre‐functionalized fullerene building blocks. 相似文献
17.
Transalkylation of Higher Trifluoromethylated Fullerenes with C70: A Pathway to New Addition Patterns of C70(CF3)8
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Nikita M. Belov Marina G. Apenova Alexey V. Rybalchenko Eugenia V. Borkovskaya Dr. Natalia S. Lukonina Dr. Alexey A. Goryunkov Dr. Ilya N. Ioffe Prof. Dr. Sergey I. Troyanov Prof. Dr. Lev N. Sidorov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1126-1133
We report three new isomers of C70(CF3)8, structurally related to p7mp‐C70(CF3)10, that are inaccessible by direct trifluoromethylation, but can be easily identified among the products of the transalkylation of higher trifluoromethylfullerenes with C70. The reported compounds are characterized by UV/Vis, 1 D and 2 D COSY 19F NMR spectroscopy, and DFT calculations. A rather unusual addition pattern is observed in p6,i‐C70(CF3)8 in which one addend is attached remotely from the others; polarization of the adjacent unsaturated bonds by the addend makes the molecule readily oxidizable. 相似文献
18.
Dr. Yang Zhang Kamran B. Ghiassi Qingming Deng Nataliya A. Samoylova Prof. Marilyn M. Olmstead Prof. Alan L. Balch Dr. Alexey A. Popov 《Angewandte Chemie (International ed. in English)》2015,54(2):495-499
The synthesis and single‐crystal X‐ray structural characterization of the first endohedral metallofullerene to contain a heptagon in the carbon cage are reported. The carbon framework surrounding the planar LaSc2N unit in LaSc2N@Cs(hept)‐C80 consists of one heptagon, 13 pentagons, and 28 hexagons. This cage is related to the most abundant Ih‐C80 isomer by one Stone–Wales‐like, heptagon/pentagon to hexagon/hexagon realignment. DFT computations predict that LaSc2N@Cs(hept)‐C80 is more stable than LaSc2N@D5h‐C80, and suggests that the low yield of the heptagon‐containing endohedral fullerene may be caused by kinetic factors. 相似文献
19.
V. Yu. Markov N. A. Samokhvalova P. S. Samokhvalov V. A. Ioutsi P. A. Khavrel’ N. S. Ovchinnikova L. N. Sidorov 《Journal of Analytical Chemistry》2010,65(14):1495-1503
Multicage fullerene cycloadducts have been detected by MALDI mass spectrometry; they have been found as admixtures in the
products of reactions of the trifluoromethylation of fullerene samples doped with metallic sodium, the reaction between fullerenes
and a mixture of trifluoromethylfullerenes, and the synthesis of fulleroproline esters. As a result, over 75 new compounds
of this type have been identified. The optimization of the synthesis procedures and chromatographic fractionation allowed
us to extract five compounds in the pure form: (C60)2(CF2)2(CF3)8, (C60)2(CF2)2(CF3)3C2F5, (C60)2(CF2)2(CF3)5C2F5, (C60)2(CF2)2(CF3)2O, and C60CH2N(CH2C60)CCOOtBu. Chemical structures of two of them, proposed on the basis of post source decay mass spectra, have been further confirmed
by NMR spectra. 相似文献
20.
Michio Yamada Dr. Mayuko Okamura Satoru Sato Chika I. Someya Naomi Mizorogi Dr. Takahiro Tsuchiya Dr. Takeshi Akasaka Prof. Tatsuhisa Kato Prof. Shigeru Nagase Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(40):10533-10542
The two regioisomers of endohedral pyrrolidinodimetallofullerenes M2@Ih‐C80(CH2)2NTrt (M=La, Ce; Trt=trityl) were synthesized, isolated, and characterized. X‐ray crystallographic analyses of [6,6]‐La2@Ih‐C80(CH2)2NTrt and [6,6]‐Ce2@Ih‐C80(CH2)2NTrt revealed that the encapsulated metal atoms are located at the slantwise positions on the mirror plane that parallels the pyrrolidine ring. Paramagnetic NMR analyses of [6,6]‐ and [5,6]‐Ce2@Ih‐C80(CH2)2NTrt were also carried out to clarify the metal positions. As for the [6,6]‐adduct, the metal positions obtained by paramagnetic NMR analysis agree well with the X‐ray structure. In contrast, paramagnetic NMR analysis of the [5,6]‐adduct showed that the two Ce atoms are collinear with the pyrrolidine ring. We also compared the observed paramagnetic effects of the pyrrolidinodimetallofullerenes with those of other cerium‐encapsulating fullerene derivatives such as bis‐silylated Ce2@Ih‐C80 and a carbene adduct of Ce2@Ih‐C80. We found that the metal positions can be explained by the electrostatic potential maps of the corresponding [6,6]‐ and [5,6]‐adducts of [Ih‐C80(CH2)2NTrt]6?. These findings clearly show that metal positions inside fullerene cages can be controlled by means of the addition positions of the addends. In addition, the radical anions of the pyrrolidinodimetallofullerenes were prepared by bulk controlled‐potential electrolysis and characterized by X‐band EPR spectral study. 相似文献