茂铁类单分子结电子传输性质的研究进展

doi:10.6023/cjoc202301002

摘要/Abstract

分子导线是构成分子器件的关键部分, 它的发展有望解决未来将要面临的电子器件尺寸即将达到理论极限而无法满足人们更高需求的问题. 茂铁类分子凭借优秀的物理、化学性质被广泛应用于非线性光学、分子电子学等领域. 在过去的十多年里, 茂铁基团的引入构建了多种结构新颖的分子导线, 为单分子器件的基础研究做出了巨大贡献. 然而对于茂铁类分子导线的研究, 大多集中于其异茂环取代的衍生物, 同茂环取代的衍生物因合成较为困难, 并没有受到研究者们的关注. 根据分子的结构特征, 将茂铁类分子导线分为π共轭型与非π共轭型两大类. 以分子的构效关系为主线, 对近十几年来茂铁类单分子结电子传输性质方面的工作进行了概括与总结, 期望为未来茂铁类分子导线的研究提供借鉴.

关键词: 茂铁类分子, 单分子结, 构效关系, 分子导线

The development of molecular wires, the key component of molecular devices and the bridge and link between electrodes, is expected to solve the problem of future electronic devices that are reaching their theoretical size limit and cannot meet the higher demands of the population. After a long period of development, molecular wires are no longer limited to the basic stages of synthesis and modification. In recent years, the exploration of the practical functions of molecular wires has been a major focus of research in molecular electronics. Ferrocene has been widely used in the fields of nonlinear optics and molecular electronics due to its excellent physical and chemical properties. In the past decade or so, the introduction of ferrocene groups has led to the construction of a variety of novel molecular wires, which have significantly contributed to the basic research of single-molecule devices. The molecular wires based on ferrocene groups have several advantages over conventional pure organic molecular wires, including (1) reduced π-π stacking between molecules, (2) adjustable molecular lengths and flexibility, (3) reduced front-line molecular orbital energy differences, which improves the electron transfer capability of molecular wires, and (4) inherently good conductive properties, which allow direct interaction with gold electrodes to form single- molecule junction. However, most of the research on ferrocene-based molecular wires has focused on their 1,1'-substituted derivatives, while their 1,3-substituted derivatives have not received much attention due to the difficulty of their synthesis. Based on the structural properties of the molecules, metallocene molecular wires are classified into two types: π-conjugated and non π-conjugated. The work on the electron transport properties of ferrocene-containing single-molecule junctions in the last decade is summarized in terms of the conformational relationships of the molecules, in the hope of providing a reference for future research on ferrocene molecular wires.

Key words: ferrocene molecules, single-molecule junction, structure-activity relationship, molecular wires

引用此文

左鑫, 许诗诺, 陈忠洋, 鄢剑锋, 袁耀锋. 茂铁类单分子结电子传输性质的研究进展[J]. 有机化学, 2023, 43(7): 2313-2322.

Xin Zuo, Shinuo Xu, Zhongyang Chen, Jianfeng Yan, Yaofeng Yuan. Research Progress of Electron Transport Properties in Ferrocene- Containing Single-Molecule Junctions[J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2313-2322.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 20

图1. 以羧酸为锚定基团的1,1'-取代茂铁类分子导线

Figure 1. 1,1'-Substituted ferrocene molecular wire connected by saturated alkane with carboxylic acid as anchor group

图2. 半胱胺封端的茂铁类分子导线

Figure 2. Cysteamine capped ferrocene molecular wires

图3. 1,1'-取代茂铁类双硫醇分子导线

Figure 3. 1,1'-Substituted ferrocene dithiol molecular wire

图4. 1,1'-取代二茂铁基二酯

Figure 4. 1,1'-Substituted ferrocenyl diester

图5. 不同长度以巯基为锚定基团通过饱和烷烃连接的1,1'-取代茂铁类分子导线

Figure 5. Different lengths of 1,1'-substituted ferrocene molecular wires connected by saturated alkane with sulfhydryl as anchor group

图6. 含多个二茂铁核的OPE型分子导线

Figure 6. OPE-type molecular wire containing multiple ferrocene cores

图7. 苯乙烯基和烷烃链连接的1,1'-取代茂铁类分子导线

Figure 7. 1,1'-Substituted ferrocene molecular wire connected by olefin and alkane chain

图8. 不同锚定基团直连的1,1'-取代茂铁类分子导线

Figure 8. 1,1'-Substituted ferrocene molecular leads with different anchoring groups directly attached

图9. 一系列OPE型茂铁类分子导线

Figure 9. A series of OPE ferrocene molecular wires

图10. 以胺基为锚定基团带有甲氧基侧链的OPE型分子导线的电阻对比

图11. 具有相同和不同锚基团的二茂铁分子导线

Figure 11. Ferrocene molecular wires with the same and different anchor groups

图12. 甲硫基封端的1,3-取代和1,1'-取代的茂铁类分子导线

Figure 12. Mercapto-terminated 1,3-substituted and 1,1'-subs- tituted ferrocene molecular wires

图13. 苯并二氢噻吩和吡啶作为锚定基团的1,1'-取代茂铁类分子导线

Figure 13. 1,1'-Substituted ferrocene molecular leads with benzo-dioxythiophene and pyridine as anchoring groups

图14. 一系列1,1'-取代茂铁类分子导线

Figure 14. A series of 1,1'-substituted ferrocene molecular wires

图15. 两种1,2,3-三取代茂铁类分子导线

Figure 15. Two 1,2,3- trisubstituted ferrocene molecular wires

图16. 通过寡聚双炔相连的双二茂铁分子导线

Figure 16. Biferrocene molecular wire connected by oligomeric diyne

图17. 拥有双导电通道的茂铁类环型分子导线

Figure 17. Ferrocene ring molecular wire with double conductive channels

图18. 二茂铁封端的寡聚噻吩分子导线

Figure 18. Ferrocene-terminated oligothiophene molecular wires and their analogues

图19. 二茂铁封端的累积烯烃(枯烯)分子导线

Figure 19. Cumulative olefin (cumene) molecular wire with ferrocene as anchor group

图20. 具有一到三个二茂铁单元的低聚茂铁类分子导线电导测试图

参考文献 48

[1]	Jeschke, G.; Sajid, M.; Schulte, M.; Ramezanian, N.; Volkov, A.; Zimmermann, H.; Godt, A. J. Am. Chem. Soc. 2010, 132, 10107. doi: 10.1021/ja102983b pmid: 20590116
[2]	Xu, X. N.; Han, B.; Yu, X.; Zhu, Y. Y. Acta Chim. Sinica 2019, 77, 485 (in Chinese). doi: 10.6023/A19010019
	(许晓娜, 韩宾, 于曦, 朱艳英, 化学学报, 2019, 77, 485.) doi: 10.6023/A19010019
[3]	Cui, X. D.; Primak, A.; Zarate, X.; Tomfohr, J.; Sankey, O. F.; Moore, A. L.; Moore, T. A.; Gust, D.; Harris, G.; Lindsay, S. M. Science 2001, 294, 571. pmid: 11641492
[4]	Venkataraman, L.; Klare, J. E.; Tam, I. W.; Nuckolls, C.; Hybertsen, M. S.; Steigerwald, M. L. Nano Lett. 2006, 6, 458. pmid: 16522042
[5]	Kubatkin, S.; Danilov, A.; Hjort, M.; Cornil, J.; Brédas, J.-L.; Stuhr-Hansen, N.; Hedegård, P.; Bjørnholm, T. Nature 2003, 425, 698. doi: 10.1038/nature02010
[6]	Venkataraman, L.; Klare, J. E.; Nuckolls, C.; Hybertsen, M. S.; Steigerwald, M. L. Nature 2006, 442, 904. doi: 10.1038/nature05037
[7]	Bigelow, W. C.; Pickett, D. L.; Zisman, W. A. J. Colloid. Sci. 1946, 1, 513. doi: 10.1016/0095-8522(46)90059-1
[8]	Liu, J.; Zhao, X.; Al-Galiby, Q.; Huang, X.; Zheng, J.; Li, R.; Huang, C.; Yang, Y.; Shi, J.; Manrique, D. Z.; Lambert, C. J.; Bryce, M. R.; Hong, W. Angew. Chem., Int. Ed. 2017, 56, 13061. doi: 10.1002/anie.201707710
[9]	Yang, G. G.; Sangtarash, S.; Liu, Z. T.; Li, X. H.; Sadeghi, H.; Tan, Z. B.; Li, R. H.; Zheng, J. T.; Dong, X. B.; Liu, J. Y.; Yang, Y.; Shi, J.; Xiao, Z. Y.; Zhang, G. X.; Lambert, C.; Hong, W. J.; Zhang, D. Q. Chem. Sci. 2017, 8, 7505. doi: 10.1039/C7SC01014A
[10]	Al, Y.; Zhang, H. L. Acta Phys.-Chim. Sin. 2012, 28, 2237 (in Chinese). doi: 10.3866/PKU.WHXB201209102
	(艾勇, 张浩力, 物理化学学报, 2012, 28, 2237.)
[11]	Frei, M.; Aradhya, S. V.; Koentopp, M.; Hybertsen, M. S.; Venkataraman, L. Nano Lett. 2011, 11, 1518. doi: 10.1021/nl1042903
[12]	Getty, S. A.; Engtrakul, C.; Wang, L.; Liu, R.; Ke, S. H.; Baranger, H. U.; Yang, W.; Fuhrer, M. S.; Sita, L. R. Phys. Rev. B 2005, 71, 4.
[13]	Astruc, D. Eur. J. Inorg. Chem. 2017, 2017, 6. doi: 10.1002/ejic.v2017.1
[14]	Sun, Y.-Y.; Peng, Z.-L.; Hou, R.; Liang, J.-H.; Zheng, J.-F.; Zhou, X.-Y.; Zhou, X.-S.; Jin, S.; Niu, Z.-J.; Mao, B.-W. Phys. Chem. Chem. Phys. 2014, 16, 2260. doi: 10.1039/c3cp53269k
[15]	Kuznetsov, A. M.; Ulstrup, J. J. Phys. Chem. A 2000, 104, 11531. doi: 10.1021/jp993635x
[16]	Kuznetsov, A. N.; Schmickler, W. Chem. Phys. 2002, 282, 371. doi: 10.1016/S0301-0104(02)00763-2
[17]	Schmickler, W.; Henderson, D. J. Electroanal. Chem. 1990, 290, 283. doi: 10.1016/0022-0728(90)87439-Q
[18]	Xiao, X. Y.; Brune, D.; He, J.; Lindsay, S.; Gorman, C. B.; Tao, N. J. Chem. Phys. 2006, 326, 138.
[19]	Zhou, X.-S.; Liu, L.; Fortgang, P.; Lefevre, A.-S.; Serra-Muns, A.; Raouafi, N.; Amatore, C.; Mao, B.-W.; Maisonhaute, E.; Schöll- horn, B. J. Am. Chem. Soc. 2011, 133, 7509. doi: 10.1021/ja201042h
[20]	Li, Y.; Haworth, N. L.; Xiang, L.; Ciampi, S.; Coote, M. L.; Tao, N. J. J. Am. Chem. Soc. 2017, 139, 14699. doi: 10.1021/jacs.7b08239
[21]	Dief, E. M.; Darwish, N. ACS Sens. 2021, 6, 573. doi: 10.1021/acssensors.0c02413
[22]	Li, Y. Q.; Wang, H.; Wang, Z. X.; Qiao, Y. J.; Ulstrup, J.; Chen, H. Y.; Zhou, G.; Tao, N. J. Proc. Natl. Acad. Sci. U. S. A. 2019, 116, 3407. doi: 10.1073/pnas.1814825116
[23]	Chen, C.-P.; Luo, W.-R.; Chen, C.-N.; Wu, S.-M.; Hsieh, S.; Chiang, C.-M.; Dong, T.-Y. Langmuir 2013, 29, 3106. doi: 10.1021/la303796r
[24]	Zhang, F.; Wu, X.-H.; Zhou, Y.-F.; Wang, Y.-H.; Zhou, X.-S.; Shao, Y.; Li, J.-F.; Jin, S.; Zheng, J.-F. ChemElectroChem 2020, 7, 1337. doi: 10.1002/celc.v7.6
[25]	Bredow, T.; Tegenkamp, C.; Pfnur, H.; Meyer, J.; Maslyuk, V. V.; Mertig, I. J. Chem. Phys. 2008, 128, 7.
[26]	Farzadi, R.; Moghaddam, H. M.; Farmanzadeh, D. Chem. Phys. Lett. 2018, 704, 37. doi: 10.1016/j.cplett.2018.05.037
[27]	Lu, Q.; Yao, C.; Wang, X. H.; Wang, F. S. J. Phys. Chem. C 2012, 116, 17853. doi: 10.1021/jp2119923
[28]	Hsung, R. P.; Chidsey, C. E. D.; Sita, L. R. Organometallics 1995, 14, 4808. doi: 10.1021/om00010a049
[29]	Engtrakul, C.; Sita, L. R. Nano Lett. 2001, 1, 541. doi: 10.1021/nl010038p
[30]	Vollmann, M.; Butenschon, H. C. R. Chim. 2005, 8, 1282. doi: 10.1016/j.crci.2005.02.019
[31]	Engtrakul, C.; Sita, L. R. Organometallics 2008, 27, 927. doi: 10.1021/om700807x
[32]	Ma, J. X.; Vollmann, M.; Menzel, H.; Pohle, S.; Butenschön, H. J. Inorg. Organomet. Polym. Mater. 2008, 18, 41. doi: 10.1007/s10904-007-9189-1
[33]	Baumgardt, I.; Butenschön, H. Eur. J. Org. Chem. 2010, 2010, 1076. doi: 10.1002/ejoc.200901252
[34]	Ma, J. X.; Krauße, N.; Butenschön, H. Eur. J. Org. Chem. 2015, 2015, 4510.
[35]	Lu, Q.; Wang, X. H.; Wang, F. S. Chin. J. Appl. Chem. 2011, 28, 136 (in Chinese).
	(路崎, 王献红, 王佛松, 应用化学, 2011, 28, 136.) doi: 10.3724/SP.J.1095.2011.00318
[36]	Lambert, C. J. Chem. Soc. Rev. 2015, 44, 875. doi: 10.1039/c4cs00203b pmid: 25255961
[37]	Zhao, X.; Stadler, R. Phys. Rev. B 2019, 99, 10. doi: 10.1103/PhysRev.99.10
[38]	Camarasa-Gómez, M.; Hernangómez-Pérez, D.; Inkpen, M. S.; Lovat, G.; Fung, E. D.; Roy, X.; Venkataraman, L.; Evers, F. Nano Lett. 2020, 20, 6381. doi: 10.1021/acs.nanolett.0c01956 pmid: 32787164
[39]	Pei, L.-Q.; Horsley, J. R.; Seng, J.-W.; Liu, X.; Yeoh, Y. Q.; Yu, M.-X.; Wu, X.-H.; Abell, A. D.; Zheng, J.-F.; Zhou, X.-S.; Yu, J.; Jin, S. ACS Appl. Mater. Interfaces 2021, 13, 57646. doi: 10.1021/acsami.1c12151
[40]	Wilkinson, L. A.; Bennett, T. L. R.; Grace, I. M.; Hamill, J.; Wang, X.; Au-Yong, S.; Ismael, A.; Jarvis, S. P.; Hou, S.; Albrecht, T.; Cohen, L. F.; Lambert, C.; Robinson, B. J.; Long, N. J. Chem. Sci. 2022, 13, 8380. doi: 10.1039/d2sc00861k pmid: 35919728
[41]	Yuan, Y.; Yan, J.-F.; Lin, D.-Q.; Mao, B.-W.; Yuan, Y.-F. Chem. - Eur. J. 2018, 24, 3545. doi: 10.1002/chem.201705176
[42]	Vazquez, H.; Skouta, R.; Schneebeli, S.; Kamenetska, M.; Breslow, R.; Venkataraman, L.; Hybertsen, M. S. Nat. Nanotechnol. 2012, 7, 663. doi: 10.1038/nnano.2012.147 pmid: 22941403
[43]	Zhao, X.; Kastlunger, G.; Stadler, R. Phys. Rev. B 2017, 96, 085421. doi: 10.1103/PhysRevB.96.085421
[44]	Takaloo, A. V.; Sadeghi, H. J. Nanosci. Nanotechnol. 2019, 19, 7452. doi: 10.1166/jnn.2019.16622
[45]	Sato, M.; Fukui, K.; Sakamoto, M.; Kashiwagi, S.; Hiroi, M. Thin Solid Films. 2001, 393, 210. doi: 10.1016/S0040-6090(01)01071-9
[46]	Bildstein, B.; Loza, O.; Chizhov, Y. Organometallics 2004, 23, 1825. doi: 10.1021/om034234d
[47]	Aragonès, A. C.; Darwish, N.; Ciampi, S.; Jiang, L.; Roesch, R.; Ruiz, E.; Nijhuis, C. A.; Díez-Pérez, I. J. Am. Chem. Soc. 2019, 141, 240. doi: 10.1021/jacs.8b09086 pmid: 30516985
[48]	Lawson, B.; Zahl, P.; Hybertsen, M. S.; Kamenetska, M. J. Am. Chem. Soc. 2022, 144, 6504. doi: 10.1021/jacs.2c01322 pmid: 35353518