富硫电子给体BVDT-TTP和BVDT-TTPY的合成，结构和性质
摘要
二十世纪70年代初合成的含4个硫原子的多硫电子给体TTF(Tetrathiafulvalene,C_6S_4H_4)型电子给体是分子导体领域中著名的电子给体。10年后TTF型电子给体的硫原子数扩充到8,例如分子超导体中首屈一指的电子给体BEDT-TTF(Bis(4,5-ethylenedithio)tetrathiafulvalene,C_(10)S_8H_8)。
近年来出现的以TTP(tetrathiapentalene,四硫并环戊烯)为结构特征的多硫电子给体是TTF体系的一个新的扩展。体现在其硫原子数目进一步增加,分子平面和共轭性更加增强。合成的难度也进一步加大,例如流程骤增,产物复杂,溶解性骤减。
本论文的研究目标是合成含12个硫原子或16个硫原子的新型多硫电子给体,为发展新一代分子导体和半导体开辟道路。我们从含2个硫原子的CS_2出发,逐步扩大分子的尺度和π共轭体系,合成了许多前体化合物。在探索反应条件方面(例如偶合反应的探索),进行了大量实验工作,完成了合成BVDT-TTP(含12个硫原子)的预定目标,并进一步合成了含16个硫原子的BVDT-TTPY。
1.首次合成含12个硫原子的多硫电子给体BVDT-TTP:
2,5-bis(4,5-vinylenedithio-1,3-dithio-2-ylidene)-1,3,4,6-tetrathiapentalene2,5-二(4,5-亚乙烯基硫-1,3-二硫-2-亚基)-1,3,4,6-四硫并环戊烯并首次测定了BVDT-TTP的分子结构和晶体结构。长度为18.6 nm的BVDT-TTP分子基本为平面构型,两端的亚乙烯基分别向上向下翘离平面,其余22个原子共平面。分子良好的平面共轭性,保证电子在分子内的充分离域。晶体中所有分子平行堆积,相邻上下分子的面间距为0.3578 nm,具有较强的分子间的π-π相互作用,有利于电子在分子间的迁移。
2.首次合成含16个硫原子的多硫电子给体BVDT-TTPY:
2,2'-bis[4,5-vinylenedithio-(1,3-dithio-2-yidene)-1,3,4,6-tetrathiapentaleneylidene]2,2'-二[(4,5-亚乙烯基硫-1,3-二硫-2-亚基)-1,3,4,6-四硫并环戊烯]
3.首次测定了VDTO-TTP的分子结构和晶体结构,它是上述BVDT-TTP和BVDT-TTPY的直接前体。
In the early 1970s,the multi-sulfur electronic donor TTF(Tetrathia-fulvalene, C_6S_4H_4)came into being as the most famous electronic donor in the area of molecular conductors.Ten years later,the number of sulfur atom in the TTFs electronic donor had been added to eight,for example,the best electronic donor in the area of molecular superconductors,the BEDT-TTF(Bis(4,5-ethylenedithio)tetrathiafulvalene,C_(10)S_8H_8).
Recently,the multi-sulfur electronic donors with TTP(tetrathiapentalene)moity are a new enlargement of the TTFs.Its sulfurs number had been farther expanded,the molecular planarity and theπ-conjugation been much improved.At the same time,the synthesis became more and more difficult,for example,the steps had to be increased and the solubility of the resultant compounds reduced sharply.
The main goal of this thesis is to synthesize the new multi-sulfur electronic donor with 12 or 16 sulfur atoms,to blaze a way in the development of new molecular conductors and molecular superconductors.We started from the CS_2 with 2 sulfurs,and enlarged the molecular dimension step by step,harvested many intermediae compounds, carried through large mumber of experiments to explore the reaction conditions(for example,the conditions of coupling reaction),and finally we successfully synthezied our target electronic donor BVDT-TTP with 12 sulfur atoms and further more the BVDT-TTPY with 16 sulfur atoms.
1.Firstly,we synthesized the electronic donor BVDT-TTP with 12 sulfur atoms.
2,5-bis(4,5-vinylenedithio-1,3-dithio-2-ylidene)-1,3,4,6-tetrathiapentalene we firstly determined the molecular strcture and crystal structure of BVDT-TTP.The BVDT-TTP molecular with the length of 18.6 nm is almost planar,except that the vinylenes on the two ends tilt from the plane.The other 22 atoms are in the same plane. The planarity andπ-conjugation make theπ-electrons delocalized on whole molecules. All of molucules in the crystal accumulate are parallely packed,the distance between two molucules is 0.3578 nm.There is quite strongπ-πinteraction between neighbouring molucules,it is good for electrons to move.
2.We firstly synthesized the electronic donor BVDT-TTPY with 16 sulfur atoms.
2,2'-bis[4,5-vinylenedithio-(1,3-dithio-2-ylidene)-1,3,4,6-tetrathiapentaleneylidene]
3.We firstly determined the molecular strcture and crystal structure of VDTO-TTP,the direct precursor of BVDT-TTP and BVDT-TTPY.
近年来出现的以TTP(tetrathiapentalene,四硫并环戊烯)为结构特征的多硫电子给体是TTF体系的一个新的扩展。体现在其硫原子数目进一步增加,分子平面和共轭性更加增强。合成的难度也进一步加大,例如流程骤增,产物复杂,溶解性骤减。
本论文的研究目标是合成含12个硫原子或16个硫原子的新型多硫电子给体,为发展新一代分子导体和半导体开辟道路。我们从含2个硫原子的CS_2出发,逐步扩大分子的尺度和π共轭体系,合成了许多前体化合物。在探索反应条件方面(例如偶合反应的探索),进行了大量实验工作,完成了合成BVDT-TTP(含12个硫原子)的预定目标,并进一步合成了含16个硫原子的BVDT-TTPY。
1.首次合成含12个硫原子的多硫电子给体BVDT-TTP:
2,5-bis(4,5-vinylenedithio-1,3-dithio-2-ylidene)-1,3,4,6-tetrathiapentalene2,5-二(4,5-亚乙烯基硫-1,3-二硫-2-亚基)-1,3,4,6-四硫并环戊烯并首次测定了BVDT-TTP的分子结构和晶体结构。长度为18.6 nm的BVDT-TTP分子基本为平面构型,两端的亚乙烯基分别向上向下翘离平面,其余22个原子共平面。分子良好的平面共轭性,保证电子在分子内的充分离域。晶体中所有分子平行堆积,相邻上下分子的面间距为0.3578 nm,具有较强的分子间的π-π相互作用,有利于电子在分子间的迁移。
2.首次合成含16个硫原子的多硫电子给体BVDT-TTPY:
2,2'-bis[4,5-vinylenedithio-(1,3-dithio-2-yidene)-1,3,4,6-tetrathiapentaleneylidene]2,2'-二[(4,5-亚乙烯基硫-1,3-二硫-2-亚基)-1,3,4,6-四硫并环戊烯]
3.首次测定了VDTO-TTP的分子结构和晶体结构,它是上述BVDT-TTP和BVDT-TTPY的直接前体。
In the early 1970s,the multi-sulfur electronic donor TTF(Tetrathia-fulvalene, C_6S_4H_4)came into being as the most famous electronic donor in the area of molecular conductors.Ten years later,the number of sulfur atom in the TTFs electronic donor had been added to eight,for example,the best electronic donor in the area of molecular superconductors,the BEDT-TTF(Bis(4,5-ethylenedithio)tetrathiafulvalene,C_(10)S_8H_8).
Recently,the multi-sulfur electronic donors with TTP(tetrathiapentalene)moity are a new enlargement of the TTFs.Its sulfurs number had been farther expanded,the molecular planarity and theπ-conjugation been much improved.At the same time,the synthesis became more and more difficult,for example,the steps had to be increased and the solubility of the resultant compounds reduced sharply.
The main goal of this thesis is to synthesize the new multi-sulfur electronic donor with 12 or 16 sulfur atoms,to blaze a way in the development of new molecular conductors and molecular superconductors.We started from the CS_2 with 2 sulfurs,and enlarged the molecular dimension step by step,harvested many intermediae compounds, carried through large mumber of experiments to explore the reaction conditions(for example,the conditions of coupling reaction),and finally we successfully synthezied our target electronic donor BVDT-TTP with 12 sulfur atoms and further more the BVDT-TTPY with 16 sulfur atoms.
1.Firstly,we synthesized the electronic donor BVDT-TTP with 12 sulfur atoms.
2,5-bis(4,5-vinylenedithio-1,3-dithio-2-ylidene)-1,3,4,6-tetrathiapentalene we firstly determined the molecular strcture and crystal structure of BVDT-TTP.The BVDT-TTP molecular with the length of 18.6 nm is almost planar,except that the vinylenes on the two ends tilt from the plane.The other 22 atoms are in the same plane. The planarity andπ-conjugation make theπ-electrons delocalized on whole molecules. All of molucules in the crystal accumulate are parallely packed,the distance between two molucules is 0.3578 nm.There is quite strongπ-πinteraction between neighbouring molucules,it is good for electrons to move.
2.We firstly synthesized the electronic donor BVDT-TTPY with 16 sulfur atoms.
2,2'-bis[4,5-vinylenedithio-(1,3-dithio-2-ylidene)-1,3,4,6-tetrathiapentaleneylidene]
3.We firstly determined the molecular strcture and crystal structure of VDTO-TTP,the direct precursor of BVDT-TTP and BVDT-TTPY.
引文
1.H.N.McCoy,W.C.Moore.Organic amalgams:substances with metallic properties composed in part of non-metallic elements.[J]J.Am.Chem.Sot.,1911,33,273.
2.W.A.Little.[J]Phys.Rev.A,1964,134,1416.
3.H.Tanaka,Y.Okano,H.Kobayashi,W.Suzuki,A.Kobayashi.A three-dimensional synthetic metallic crystal composed of single-component molecular.[J]Science.2001.Vol 291.285-287.
4.M.Ashizawa,S.Kimura,T.Mori,Y.Misaki,and K.Tanaka.Tris-fused tetrathiafulval-enes(TTF):highly conducting single-component organics and metallic charge-transfer salt.[J]Synthetic Metals.,2004,14,307-313
5..W.E.Cooper,N.C.Kenny,J.W.Edmonds,A.Nagei,F.Wudl,and P.Coppens.[J].Chem.Soc.Chem.Commun.1971.15.889-890
6.D.S.Acker,R.J.Harder,W.R.Hertler,W.Mahler,L.R.Melby,R.E.Benson,W.E.Mochel.7,7,8,8-Tetracyanoquinodimethane and its electrically conducting anion-radical derivatives.[J]J.Am.Chem.Soc.,1960,82,6408-9.
7.(a)E Wudl,G.M.Smith,E.J.Hufnagel.1,3-Bisdithiole Chloride.[J]Chem.Commun.,1970,1453-1454.
(b)F.Wudl,D.Wobschall,E.J.Hufnagel.Electrical conductivity by the bis(1,3-dithiole)-bis(1,3- dithiolium)system.[J]J.Am.Chem.Soc.,1972,94,670-672
8.J.P.Ferraris,D.O.Cowan,V.Valatka,J.H.Perlstein.Electron transfer in a new highly conducting donor-acceptor complex.[J]J.Am.Chem.Soc.,1973,95,948-949.
9.K.Bechgaard,D.O.Cowan,A.N.Bloch.[J]Chem.Commun.,1974,937.
10.K.Bechgaard,K.Carneiro,F.G.Rasmussen,K.Olsen,G.Rindorf,C.S.Jacobsen,H.J. Pedersen, and J. E. Scott. Superconductivity in an organic solid Synthesis, structure, and conductivity of bis(tetramethyltetraselenafulvalenium) perchlorate, (TMTSF)_2ClO_4. [J] J. Am. Chem. Soc, 1981, 103, 2440-2442
11. T. Otsubo and K. Takimiya. Recent synthetic advances of tetrathiafulvalene-based organic conductors. [J] Bull. Chem. Soc. Jpn., 2004, 77,43-58.
12. M. Mizuno, A. F. Garito, M. P. Cava.[J] Chem. Commun., 1978,18.
13. (a) J. M. Williams, M. A. Beno, H. H. Wang, P. E. Reed, L. J. Azevedo, J. E. Schirber. Synthetic metals based on bis(ethylenedithio)tetrathiafulvalene: synthesis, structure (T = 298 and 125 K) and NMR of (BEDT-TTF)_2X, X = ReO_4~- and BrO_4~-.[J] Inorg. Chem., 1984, 25(13), 1790-1792. (b) S. S. P. Parkin, E. M. Engler, R. R. Schumaker, R. Lagier, V. Y. Lee, J. C. Scott,and R. L. Greene. Superconductivity in a New Family of Organic Conductors. [J] Phys. Rev. Lett. 1983, 5,270-273.
14. J. M. Williams, T. J. Emge, H. H. Wang, M. A. Beno, P. T. Copps, L. N. Hall, K. D. Carlson, G. W. Crabtree. Synthetic metals based on bis(ethylenedithio) tetrathiafulvalene (ET): synthesis, structure, and ambient-pressure superconductivity in (ET)_2I_3. [J]Inorg. Chem., 1984,23(17), 2558-2560.
15. J. M. Williams, H. H. Wang, M. A. Beno, et al. Ambient-pressure superconductivity at 2.7 K and higher temperatures in derivatives of (BEDT-TTF)_2IBr_2: synthesis, structure, and detection of superconductivity.[J] Inorg. Chem., 1984,23, 3839-3841.
16. H.H. Wang, M.A. Beno, U. Geiser, M.A. Firestone, K.S. Webb, L. Nunez, GW.Crabtree, K.D. Carlson, J.M. Williams. Ambient-pressure superconductivity at the highest temperature (5 K) observed in an organic system: β-(ET)_2AuI_2.[J] Inorg. Chem., 1985,24,2465-2466.
17. H. Urayama, H. Yamochi, G Saito, K. Nozawa, T. Sugano, M. Kinoshita, S. Sato, K. Oshima, A. Kawamoto and J. Tanaka. [J] Chem.Lett.1988, 55
18. A. M. Kini, U. Geiser, H. H. Wang, K. D. Carlson, J. M. Williams, W. K. Kwok, K. G Vandervoort, J. E. Thompson, D. L. Stupka, D. Jung and M. H. Whangbo. [J] Inog.Chem., 1990,29,2555
19. N. D. Kusuch, M. A. Tanatar, E. B. Yagubskii and T. Ishiguro. [J] JETP Lett., 2001,73, 429
20. T. Nakamura, S. I. Iwasaka, H. Nakano, K. Inoue, T. Nogami and H. mikawa. Syntheses of bis(vinylenedithio)tetrathiafulvalene and bis(methylvinylenedithio)- tetra-thiafulvalene.[J] Bull. Chem. Soc. Jpn., 1987, 60. 365-368
21. A. M. Kini. [J] Solid State Commun. 1989, 69, 503.
22. K. Takimiya, Y. Kataoka, Y. Aso, T. Otsubo, H. Fukuoka, S. Yamanaka. Quasi One-Dimensional Organic Superconductor MDT-TSF-AuI_2 with T_c=4.5 K at Ambient Pressure.[J] Angew. Chem. Int. Ed., 2001, 40(6), 1122-1125.
23. Y. Misaki, H. Fujiwara, T. Yamabe, T. Mori, H. Mori, and S. Tanaka. Structure and conducting properties of BDT-TTP salts. [J] Chem. Lett. 1994. pp. 1653-1656
24. J. Yamada, M. Watanabe, H. Akutsu, S. Nakatsuji, H. Nishikawa, I. Ikemoto and K. Kikuchi. BDH-TTP as a structural isomer of BEDT-TTF, and its two-dimensional hexafluorophosphate salts. [J] Angew. Chem. Int. Ed. 1999, 38
25.J.Yamada,M.Watanabe,H.Akutsu,S.Nakatsuji,H.Nishikawa,I.Ikemoto and K.Kikuchi.New organic superconductors β-(BDA-TTP)_2X[BDA-TTP=2,5-bis-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene;X~-=SbF_6~-,AsF_6~-,and PF_6~-].[J]J.Am.Chem.Soc.,2001,123,4174-4180
26.J.Yamada,T.Toita,H.Akutsu,S.Nakatsuji,H.Nishikawa,I.Ikemoto,K.Kikuchi,E.S.Choi,D.Graf,and J.S.Brooks.A new organic superconductor,β-(BDA-TTP)_2GaCl_4[BDA-TTP=2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetra-thiapentalene].[J]Chem.Cummun.2003.2230-2231
27.J.Yamada,T.Toita,H.Akutsu,S.Nakatsuji,H.Nishikawa,I.Ikemoto,and K.Kikuchi.The crystal structure and physical properties of β-(BDA-TTP)_2FeCl_4[BDA-TTP =2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene].[J]Chem.Cummun.2001.2538-2539.
28.T.Mori,Y.Misaki,H.Fujiwara,and T.Yamabe.Crystal structure and physical properties of(BDT-TTP)_2ClO_4.[J]Bull.Chem.Soc.Jpn.,1994,67,2685-2689
29.H.B.Cui,T.Otsuka,A.Kobayashi,Y.Misaki,and H.Kobayashi.Structural and electrical properties of novel molecular conductors based on extended-TTF donors BDT-TTP and I~- anions.[J]Bull.Chem.Soc.Jpn.,2003,76,97-102
30.Y.Misaki,H.Nishikawa,K.Kawakami,S.Koyanagi,T.Yamabe,M.Shiro.Chem.Lett.1992.2321
31.T.Mori,T.Kawamoto,Y.Misaki,and K.Tanaka.Novel one-dimensional organic conductor based on selenium-containing bis-fused tetrathiafulvalene derivative,(TSM-TTP)(I_3)_(5/3).[J]Bull.Chem.Soc.Jpn.,1998,71,1321-1326
32.S.Kimura,H.Kurai,and T.Mori.2,5-Bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapen-talene (TTP)derivatives having four long alkylthio chains.[J]Tetrahedron.,2002,58,1119-1124
33.T.Mori,H.Inokuchi,Y.Misaki,H.Nishikawa,T.Yamabe,H.Mori,and S.Tanaka.Structure and physical properties of(TMET-TTP)_2Au(CN)_2.[J]Chem.Lett.,1993,pp.2085-2088
34.Y.Misaki,H.Nishikawa,T.Yamabe,T.Mori,and H.Inokuchi.Crystal structures of TMEO-TTP and(TMEO-TTP)[AuBr_2]THF.[J]Bull.Chem.Soc.Jpn.,1994.2368-2372.
35.M.Aragaki,S.Kimura,M.Katsuhara,H.Kurai,and T.Moil.Selenium analogs of tetrathiapentalene derivatives with long alkyl chains.[J]Bull Chem.Soc.Jpn.,2001,74,833-838
36.S.Kimura,S.Hanazato,H.Kurai,T.Moil,Y.Misaki,and K.Tanaka.Stereo-chemically ordered donor columns in an organic conductor,(Et_2BEDT-TTP)_2HgI_3.[J]Tetrahedron.Lett.,2001,42,5729-5732.
37.Y.Misaki,K.Tanaka,M.Taniguchi,T.Yamabe,T.Kawamoto,and T.Moil.Structures and electrical properties of(EO-TTP)_2AsF_6.[J]Chem.Lett.,1999,1249-1250
38.Y.Misaki,K.Tanaka,M.Taniguchi,T.Yamabe,and T.Moil.Structures and properties of a new K-type organic metal:(CPEO-TTP)(SbF6)0.4.[J]Adv.Mater.1999.11.25-27.
39.H.Nishikawa,S.Kawauchi,Y.Misaki,and T.Yaamabe.Synthesis and properties of alkylthio-substituted tris-fused tetrathiafulvalenes.[J]Chem.Lett.,1996,43-44
40.J.P.M.Nunes,M.J.Figueira,D.Belo,I.C.Santos,B.Ribeiro,E.B.Lopes,R.F.Henriques,J.V-Gancedo,J.Veciana,C.Rovira,and M.Almeida.Transition metal bisdithiolene complexes based on extended ligands with fused tetrathiafulvalene and thiophene moieties:new single-component molecular metals.[J]Chem.Eur.J.,2007,13,9841-9849
41.Y.Yamashita,T.Suzuki,and T.Miyashi.2,2'-(5,8-Dihydroquinoxaline-5,8-diylidene)bis(1,3-benzodithiole)s.A new type of electron donors.[J]Chem.Lett.,1989,pp.1607-1610.
42.K.Sako,H.Ok-u,Y.Misaki,K.Tanaka,H.Tatemitsu.Synthesis and properties of π-extended donors with crown ether units.[J]Synthetic Metals.,2003,137,901-902
43.E.Demiralp.Structural and electronic properties of novel nanaoscale C4nS4n molecules.[J]Journal of Molecular Structure(Theochem).,2003,635,125-131.
44.A.Tsumura,H.Koezuka,and T.Ando.Macromolecular electronic device:Field-effect transistor with a polythiophene thin film.[J]Appl.Phys.Lett.,1986,49(18),1210-1212
45.M.M-Torrent,S.Masirek,P.Hadley,N.Crivillers,N.S.Oxtoby,P.Reuter,J.Veciana,C.Rovira,and A.Tracz.Organic field-effect transistors(OFETs)of highly oriented films of dithiophene-tetrathiafulvalene prepared by zone casting.[J]Organic Electronics.,2008,9,143-148.
1.S.Wang,A.S.Batsanov,M.R.Bryce,J.A.K.Howard.An improved,large-scale(90g)synthesis of bis(tetrathylammonium)bis(1,3-dithiole-2-thione-4,5- dithiol)zincate:synthesis and X-ray crystal structures of bicyclic and tricyclic 1,4-dithiocines derived from 1,3-dithiol-2-thione-4,5-dithiolate(DMIT).[J].Synthesis.,1998,1615-1618
2.Nakamura,S.-I.Iwasaka,H.Nakano,K.Inoue,T.Nogami,and H.Mikawa.Syntheses of bis(vinylenedithio)tetrathiafulvalene and bia(methylvinylenedithio)-tetrathiafulvalene.[J].Bull.Chem.Soc.Jpn.,1987,60,365-368
3.R.Andreu,J.Garin,J.Orduna,and J.M.Royo.On the mechanism of formation of 1,4,5,8-tetrathianaphthalene(TTN)from dimercaptoisotrithione(dmit)derivatives.Tetrahedron.[J].Letters.,2000,41,5207-5210
4.K.S.Varma,and A.E.Underhill.Synthetic studies on extended S-donor ligands as potential molecular conductions.[J].Physica.1986.143B.321-323
5.N.Svenstrup,K.M.Rasmussen,T.K.Hansen,and J.Becher.The chemistry of TTFTT;1:new efficient synthesis and reactions of tetrathiafulvalene-2,3,6,7- tetrathiolate (TTFTT):an important building block in TTF-synthesis[J].Synthesis.,1994,809-811
1.M.Aragaki,T.Mori,Y.Misaki,K.Tanaka,T.Yamabe.Facile preparaton of TTP series donors by usingcyanoethyl groups.[J]Syn.Metals.1999.102.1601-1602
2.M.Yohji,N.Hiroyuki,K.Kazuya,K.Shiro,Y.Tokio,S.Motoo.Methylthio substituted 2,5-bis(1,3-dithiol-2-ylidene)- 1,3,4,6-tetrathiapentalene a his-fused tetrathiafulvalene.[J]Chem.Lett.1992.2321-2324
3.中西香而.P.H.索罗曼著.王绪明译.红外光谱分析100例.科学出版社.1984.
1.Y.Misaki,H.Nishikawa,K.Kawakami,S.Koyanagi,T.Yamabe,and M.Shiro.Methylthio substituted 2,5-his(1',3'-dithiol-2'2ylidene)- 1,3,4,6-tetrathiapentalene a bis-fused tetrathiafulvalene.[J]Chem.Lett.1992.2321-2324.
2.S.Kimura,H.Nii,H.Kurai,T.Takeuchi,M.Katsuhara,and T.Mori.Ethylenedioxy-containing tetrathiapentalene derivative with ethylthio chains,C_2TEO-TTE[J]Bull.Chem.Soc.Jpn.,2003.76.89-96.
3.T.Nakamura,S.Iwasaka,H.Nakano,K.Inoue,T.Nogami,and H.Mikawa.Syntheses of bis(vinylenedithio)tetrathiafulvalene and bis(methyvinylenedithio)tetrathiafulval- ene.[J]Bull.Chem.Soc.Jpn.,1987.60.365-368.
4.N.Svenstrup,K.M.Rasmussen,T.K.Hansen,J.Becher.The chemistry of TTFTT;1:new efficient Synthesis and reactions of tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFTT):an important building block in TTF-syntheses.[J].Synthesis.,1994,809-811
5.L.P.Wu,J.Dai,M.Munakata,T.Kurada-Sowa,M.Maekawa,Y.Suenaga,and Y.Ohno,S…S Contact-assembled tetrathiafulvalene derivatives of copper(Ⅰ)and silver(Ⅰ)co-ordination polymers and organic radical cation salt
6.L.Binet,J.M.Fabre,C.Montginoul,K.B.Simonsen,and J.Becher.Preparation and chemistry of new unsymmetrically substituted tetrachalcogenofulvalenes beating CN(CH_2)_2X and HO(CH_2)_2X groups(X=S or Se).[J].J.Chem.Sot.,Perkin.Trans.I.1996.783-788.
7.K.Sako,H.Oku,Y.Misaki,K.Tanaka,and H.Tatemitsu.Synthesis and properties of π-extended donors with crown t\ether units.[J].Synthetic Metals.2003.137.901-902.
8.M.Ashizawa,S.Kimura,T.Mori,Y.Misaki,and K.Tanaka.Tris-fused tetrathiafulvalenes (TTF):highly conducting single-component organics and metallic charge-transfer salt.[J].Syntketic.Metals.2004.141.307-313
9.Y.Misaki,H.Nishikawa,T.Yamabe,T.Mori,H.Inokuchi.Bis(methylthio)substituted unsymmetrical 2,5-bis(l',3'-dithiol-2'-ylidene)-l,3,4,6-tetrathiapentalenes.[J].Chem.Lett.1993.pp.729-732
10.M.Aragaki,S.Kimura,M.Katsuhara,H.Kurai,and T.Mori.Selenium analogs of tetrathiapentalene derivatives with long alkyl chains.[J]Bull.Ckem.Soc.Jpn.,2001,74,833-838
11.H.Yamochi,G.Saito.Synthesis of symmetrically substituted bis-TTF fused 1,4-dithiine(BTDT)derivatives.[J]Synthetic Metals.1997.85.1467-1468.
12.H-Y.Chen,W-T.Yu,G.Xue,and Q.Fang.Dimethyl 5,6-dihydro-2H-1,3-dithiolo[4,5-b][1,4]dithiin-2-ylphosphonate.[J]Acta.Cryst.2005.E61.1400-1402.
2.W.A.Little.[J]Phys.Rev.A,1964,134,1416.
3.H.Tanaka,Y.Okano,H.Kobayashi,W.Suzuki,A.Kobayashi.A three-dimensional synthetic metallic crystal composed of single-component molecular.[J]Science.2001.Vol 291.285-287.
4.M.Ashizawa,S.Kimura,T.Mori,Y.Misaki,and K.Tanaka.Tris-fused tetrathiafulval-enes(TTF):highly conducting single-component organics and metallic charge-transfer salt.[J]Synthetic Metals.,2004,14,307-313
5..W.E.Cooper,N.C.Kenny,J.W.Edmonds,A.Nagei,F.Wudl,and P.Coppens.[J].Chem.Soc.Chem.Commun.1971.15.889-890
6.D.S.Acker,R.J.Harder,W.R.Hertler,W.Mahler,L.R.Melby,R.E.Benson,W.E.Mochel.7,7,8,8-Tetracyanoquinodimethane and its electrically conducting anion-radical derivatives.[J]J.Am.Chem.Soc.,1960,82,6408-9.
7.(a)E Wudl,G.M.Smith,E.J.Hufnagel.1,3-Bisdithiole Chloride.[J]Chem.Commun.,1970,1453-1454.
(b)F.Wudl,D.Wobschall,E.J.Hufnagel.Electrical conductivity by the bis(1,3-dithiole)-bis(1,3- dithiolium)system.[J]J.Am.Chem.Soc.,1972,94,670-672
8.J.P.Ferraris,D.O.Cowan,V.Valatka,J.H.Perlstein.Electron transfer in a new highly conducting donor-acceptor complex.[J]J.Am.Chem.Soc.,1973,95,948-949.
9.K.Bechgaard,D.O.Cowan,A.N.Bloch.[J]Chem.Commun.,1974,937.
10.K.Bechgaard,K.Carneiro,F.G.Rasmussen,K.Olsen,G.Rindorf,C.S.Jacobsen,H.J. Pedersen, and J. E. Scott. Superconductivity in an organic solid Synthesis, structure, and conductivity of bis(tetramethyltetraselenafulvalenium) perchlorate, (TMTSF)_2ClO_4. [J] J. Am. Chem. Soc, 1981, 103, 2440-2442
11. T. Otsubo and K. Takimiya. Recent synthetic advances of tetrathiafulvalene-based organic conductors. [J] Bull. Chem. Soc. Jpn., 2004, 77,43-58.
12. M. Mizuno, A. F. Garito, M. P. Cava.[J] Chem. Commun., 1978,18.
13. (a) J. M. Williams, M. A. Beno, H. H. Wang, P. E. Reed, L. J. Azevedo, J. E. Schirber. Synthetic metals based on bis(ethylenedithio)tetrathiafulvalene: synthesis, structure (T = 298 and 125 K) and NMR of (BEDT-TTF)_2X, X = ReO_4~- and BrO_4~-.[J] Inorg. Chem., 1984, 25(13), 1790-1792. (b) S. S. P. Parkin, E. M. Engler, R. R. Schumaker, R. Lagier, V. Y. Lee, J. C. Scott,and R. L. Greene. Superconductivity in a New Family of Organic Conductors. [J] Phys. Rev. Lett. 1983, 5,270-273.
14. J. M. Williams, T. J. Emge, H. H. Wang, M. A. Beno, P. T. Copps, L. N. Hall, K. D. Carlson, G. W. Crabtree. Synthetic metals based on bis(ethylenedithio) tetrathiafulvalene (ET): synthesis, structure, and ambient-pressure superconductivity in (ET)_2I_3. [J]Inorg. Chem., 1984,23(17), 2558-2560.
15. J. M. Williams, H. H. Wang, M. A. Beno, et al. Ambient-pressure superconductivity at 2.7 K and higher temperatures in derivatives of (BEDT-TTF)_2IBr_2: synthesis, structure, and detection of superconductivity.[J] Inorg. Chem., 1984,23, 3839-3841.
16. H.H. Wang, M.A. Beno, U. Geiser, M.A. Firestone, K.S. Webb, L. Nunez, GW.Crabtree, K.D. Carlson, J.M. Williams. Ambient-pressure superconductivity at the highest temperature (5 K) observed in an organic system: β-(ET)_2AuI_2.[J] Inorg. Chem., 1985,24,2465-2466.
17. H. Urayama, H. Yamochi, G Saito, K. Nozawa, T. Sugano, M. Kinoshita, S. Sato, K. Oshima, A. Kawamoto and J. Tanaka. [J] Chem.Lett.1988, 55
18. A. M. Kini, U. Geiser, H. H. Wang, K. D. Carlson, J. M. Williams, W. K. Kwok, K. G Vandervoort, J. E. Thompson, D. L. Stupka, D. Jung and M. H. Whangbo. [J] Inog.Chem., 1990,29,2555
19. N. D. Kusuch, M. A. Tanatar, E. B. Yagubskii and T. Ishiguro. [J] JETP Lett., 2001,73, 429
20. T. Nakamura, S. I. Iwasaka, H. Nakano, K. Inoue, T. Nogami and H. mikawa. Syntheses of bis(vinylenedithio)tetrathiafulvalene and bis(methylvinylenedithio)- tetra-thiafulvalene.[J] Bull. Chem. Soc. Jpn., 1987, 60. 365-368
21. A. M. Kini. [J] Solid State Commun. 1989, 69, 503.
22. K. Takimiya, Y. Kataoka, Y. Aso, T. Otsubo, H. Fukuoka, S. Yamanaka. Quasi One-Dimensional Organic Superconductor MDT-TSF-AuI_2 with T_c=4.5 K at Ambient Pressure.[J] Angew. Chem. Int. Ed., 2001, 40(6), 1122-1125.
23. Y. Misaki, H. Fujiwara, T. Yamabe, T. Mori, H. Mori, and S. Tanaka. Structure and conducting properties of BDT-TTP salts. [J] Chem. Lett. 1994. pp. 1653-1656
24. J. Yamada, M. Watanabe, H. Akutsu, S. Nakatsuji, H. Nishikawa, I. Ikemoto and K. Kikuchi. BDH-TTP as a structural isomer of BEDT-TTF, and its two-dimensional hexafluorophosphate salts. [J] Angew. Chem. Int. Ed. 1999, 38
25.J.Yamada,M.Watanabe,H.Akutsu,S.Nakatsuji,H.Nishikawa,I.Ikemoto and K.Kikuchi.New organic superconductors β-(BDA-TTP)_2X[BDA-TTP=2,5-bis-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene;X~-=SbF_6~-,AsF_6~-,and PF_6~-].[J]J.Am.Chem.Soc.,2001,123,4174-4180
26.J.Yamada,T.Toita,H.Akutsu,S.Nakatsuji,H.Nishikawa,I.Ikemoto,K.Kikuchi,E.S.Choi,D.Graf,and J.S.Brooks.A new organic superconductor,β-(BDA-TTP)_2GaCl_4[BDA-TTP=2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetra-thiapentalene].[J]Chem.Cummun.2003.2230-2231
27.J.Yamada,T.Toita,H.Akutsu,S.Nakatsuji,H.Nishikawa,I.Ikemoto,and K.Kikuchi.The crystal structure and physical properties of β-(BDA-TTP)_2FeCl_4[BDA-TTP =2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene].[J]Chem.Cummun.2001.2538-2539.
28.T.Mori,Y.Misaki,H.Fujiwara,and T.Yamabe.Crystal structure and physical properties of(BDT-TTP)_2ClO_4.[J]Bull.Chem.Soc.Jpn.,1994,67,2685-2689
29.H.B.Cui,T.Otsuka,A.Kobayashi,Y.Misaki,and H.Kobayashi.Structural and electrical properties of novel molecular conductors based on extended-TTF donors BDT-TTP and I~- anions.[J]Bull.Chem.Soc.Jpn.,2003,76,97-102
30.Y.Misaki,H.Nishikawa,K.Kawakami,S.Koyanagi,T.Yamabe,M.Shiro.Chem.Lett.1992.2321
31.T.Mori,T.Kawamoto,Y.Misaki,and K.Tanaka.Novel one-dimensional organic conductor based on selenium-containing bis-fused tetrathiafulvalene derivative,(TSM-TTP)(I_3)_(5/3).[J]Bull.Chem.Soc.Jpn.,1998,71,1321-1326
32.S.Kimura,H.Kurai,and T.Mori.2,5-Bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapen-talene (TTP)derivatives having four long alkylthio chains.[J]Tetrahedron.,2002,58,1119-1124
33.T.Mori,H.Inokuchi,Y.Misaki,H.Nishikawa,T.Yamabe,H.Mori,and S.Tanaka.Structure and physical properties of(TMET-TTP)_2Au(CN)_2.[J]Chem.Lett.,1993,pp.2085-2088
34.Y.Misaki,H.Nishikawa,T.Yamabe,T.Mori,and H.Inokuchi.Crystal structures of TMEO-TTP and(TMEO-TTP)[AuBr_2]THF.[J]Bull.Chem.Soc.Jpn.,1994.2368-2372.
35.M.Aragaki,S.Kimura,M.Katsuhara,H.Kurai,and T.Moil.Selenium analogs of tetrathiapentalene derivatives with long alkyl chains.[J]Bull Chem.Soc.Jpn.,2001,74,833-838
36.S.Kimura,S.Hanazato,H.Kurai,T.Moil,Y.Misaki,and K.Tanaka.Stereo-chemically ordered donor columns in an organic conductor,(Et_2BEDT-TTP)_2HgI_3.[J]Tetrahedron.Lett.,2001,42,5729-5732.
37.Y.Misaki,K.Tanaka,M.Taniguchi,T.Yamabe,T.Kawamoto,and T.Moil.Structures and electrical properties of(EO-TTP)_2AsF_6.[J]Chem.Lett.,1999,1249-1250
38.Y.Misaki,K.Tanaka,M.Taniguchi,T.Yamabe,and T.Moil.Structures and properties of a new K-type organic metal:(CPEO-TTP)(SbF6)0.4.[J]Adv.Mater.1999.11.25-27.
39.H.Nishikawa,S.Kawauchi,Y.Misaki,and T.Yaamabe.Synthesis and properties of alkylthio-substituted tris-fused tetrathiafulvalenes.[J]Chem.Lett.,1996,43-44
40.J.P.M.Nunes,M.J.Figueira,D.Belo,I.C.Santos,B.Ribeiro,E.B.Lopes,R.F.Henriques,J.V-Gancedo,J.Veciana,C.Rovira,and M.Almeida.Transition metal bisdithiolene complexes based on extended ligands with fused tetrathiafulvalene and thiophene moieties:new single-component molecular metals.[J]Chem.Eur.J.,2007,13,9841-9849
41.Y.Yamashita,T.Suzuki,and T.Miyashi.2,2'-(5,8-Dihydroquinoxaline-5,8-diylidene)bis(1,3-benzodithiole)s.A new type of electron donors.[J]Chem.Lett.,1989,pp.1607-1610.
42.K.Sako,H.Ok-u,Y.Misaki,K.Tanaka,H.Tatemitsu.Synthesis and properties of π-extended donors with crown ether units.[J]Synthetic Metals.,2003,137,901-902
43.E.Demiralp.Structural and electronic properties of novel nanaoscale C4nS4n molecules.[J]Journal of Molecular Structure(Theochem).,2003,635,125-131.
44.A.Tsumura,H.Koezuka,and T.Ando.Macromolecular electronic device:Field-effect transistor with a polythiophene thin film.[J]Appl.Phys.Lett.,1986,49(18),1210-1212
45.M.M-Torrent,S.Masirek,P.Hadley,N.Crivillers,N.S.Oxtoby,P.Reuter,J.Veciana,C.Rovira,and A.Tracz.Organic field-effect transistors(OFETs)of highly oriented films of dithiophene-tetrathiafulvalene prepared by zone casting.[J]Organic Electronics.,2008,9,143-148.
1.S.Wang,A.S.Batsanov,M.R.Bryce,J.A.K.Howard.An improved,large-scale(90g)synthesis of bis(tetrathylammonium)bis(1,3-dithiole-2-thione-4,5- dithiol)zincate:synthesis and X-ray crystal structures of bicyclic and tricyclic 1,4-dithiocines derived from 1,3-dithiol-2-thione-4,5-dithiolate(DMIT).[J].Synthesis.,1998,1615-1618
2.Nakamura,S.-I.Iwasaka,H.Nakano,K.Inoue,T.Nogami,and H.Mikawa.Syntheses of bis(vinylenedithio)tetrathiafulvalene and bia(methylvinylenedithio)-tetrathiafulvalene.[J].Bull.Chem.Soc.Jpn.,1987,60,365-368
3.R.Andreu,J.Garin,J.Orduna,and J.M.Royo.On the mechanism of formation of 1,4,5,8-tetrathianaphthalene(TTN)from dimercaptoisotrithione(dmit)derivatives.Tetrahedron.[J].Letters.,2000,41,5207-5210
4.K.S.Varma,and A.E.Underhill.Synthetic studies on extended S-donor ligands as potential molecular conductions.[J].Physica.1986.143B.321-323
5.N.Svenstrup,K.M.Rasmussen,T.K.Hansen,and J.Becher.The chemistry of TTFTT;1:new efficient synthesis and reactions of tetrathiafulvalene-2,3,6,7- tetrathiolate (TTFTT):an important building block in TTF-synthesis[J].Synthesis.,1994,809-811
1.M.Aragaki,T.Mori,Y.Misaki,K.Tanaka,T.Yamabe.Facile preparaton of TTP series donors by usingcyanoethyl groups.[J]Syn.Metals.1999.102.1601-1602
2.M.Yohji,N.Hiroyuki,K.Kazuya,K.Shiro,Y.Tokio,S.Motoo.Methylthio substituted 2,5-bis(1,3-dithiol-2-ylidene)- 1,3,4,6-tetrathiapentalene a his-fused tetrathiafulvalene.[J]Chem.Lett.1992.2321-2324
3.中西香而.P.H.索罗曼著.王绪明译.红外光谱分析100例.科学出版社.1984.
1.Y.Misaki,H.Nishikawa,K.Kawakami,S.Koyanagi,T.Yamabe,and M.Shiro.Methylthio substituted 2,5-his(1',3'-dithiol-2'2ylidene)- 1,3,4,6-tetrathiapentalene a bis-fused tetrathiafulvalene.[J]Chem.Lett.1992.2321-2324.
2.S.Kimura,H.Nii,H.Kurai,T.Takeuchi,M.Katsuhara,and T.Mori.Ethylenedioxy-containing tetrathiapentalene derivative with ethylthio chains,C_2TEO-TTE[J]Bull.Chem.Soc.Jpn.,2003.76.89-96.
3.T.Nakamura,S.Iwasaka,H.Nakano,K.Inoue,T.Nogami,and H.Mikawa.Syntheses of bis(vinylenedithio)tetrathiafulvalene and bis(methyvinylenedithio)tetrathiafulval- ene.[J]Bull.Chem.Soc.Jpn.,1987.60.365-368.
4.N.Svenstrup,K.M.Rasmussen,T.K.Hansen,J.Becher.The chemistry of TTFTT;1:new efficient Synthesis and reactions of tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFTT):an important building block in TTF-syntheses.[J].Synthesis.,1994,809-811
5.L.P.Wu,J.Dai,M.Munakata,T.Kurada-Sowa,M.Maekawa,Y.Suenaga,and Y.Ohno,S…S Contact-assembled tetrathiafulvalene derivatives of copper(Ⅰ)and silver(Ⅰ)co-ordination polymers and organic radical cation salt
6.L.Binet,J.M.Fabre,C.Montginoul,K.B.Simonsen,and J.Becher.Preparation and chemistry of new unsymmetrically substituted tetrachalcogenofulvalenes beating CN(CH_2)_2X and HO(CH_2)_2X groups(X=S or Se).[J].J.Chem.Sot.,Perkin.Trans.I.1996.783-788.
7.K.Sako,H.Oku,Y.Misaki,K.Tanaka,and H.Tatemitsu.Synthesis and properties of π-extended donors with crown t\ether units.[J].Synthetic Metals.2003.137.901-902.
8.M.Ashizawa,S.Kimura,T.Mori,Y.Misaki,and K.Tanaka.Tris-fused tetrathiafulvalenes (TTF):highly conducting single-component organics and metallic charge-transfer salt.[J].Syntketic.Metals.2004.141.307-313
9.Y.Misaki,H.Nishikawa,T.Yamabe,T.Mori,H.Inokuchi.Bis(methylthio)substituted unsymmetrical 2,5-bis(l',3'-dithiol-2'-ylidene)-l,3,4,6-tetrathiapentalenes.[J].Chem.Lett.1993.pp.729-732
10.M.Aragaki,S.Kimura,M.Katsuhara,H.Kurai,and T.Mori.Selenium analogs of tetrathiapentalene derivatives with long alkyl chains.[J]Bull.Ckem.Soc.Jpn.,2001,74,833-838
11.H.Yamochi,G.Saito.Synthesis of symmetrically substituted bis-TTF fused 1,4-dithiine(BTDT)derivatives.[J]Synthetic Metals.1997.85.1467-1468.
12.H-Y.Chen,W-T.Yu,G.Xue,and Q.Fang.Dimethyl 5,6-dihydro-2H-1,3-dithiolo[4,5-b][1,4]dithiin-2-ylphosphonate.[J]Acta.Cryst.2005.E61.1400-1402.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |