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Metal-phthalocyanines (MPcs) and their derivates have attracted increasing interest in recent years, due to their potential applications in molecular electronics, spintronics, sensors, and so on. To this end, it is essential to tune the structural, electronic and spin properties of MPcs. Using the low-temperature scanning tunneling microscopy (LT-STM), we demonstrate that the spin, chirality and adsorption site of MnPc on Au(111) surface can be tuned by hydrogen atoms. STM experiments and density functional theory (DFT) calculations reveal that the preferential adsorption sites for the MnPc molecules may switch from the fcc regions to the hcp regions on the Au(111) surface after a hydrogen atom is adsorbed on top of the central Mn ion of each MnPc molecule. Moreover, the molecular spin decreases from S=3/2 to S=1 and the molecule-substrate coupling is weakened after the adsorption of a hydrogen atom on a MnPc molecule, leading to the quenching of Kondo effect at 4.2 K. However, the molecular spin and Kondo effect can be recovered by local voltage pulse or sample heating. Adsorption of three hydrogen atoms on a MnPc molecule not merely lowers the molecular symmetry from 4-to 2-fold, but also breaks down the mirror symmetry of the entire adsorbate complex (molecule and surface), thus rendering it to become chiral without any realignment at the surface. Dehydrogenation of the adsorbate by means of inelastic electron tunneling can also restore the mirror symmetry of the adsorbate complex. STM experiments as well as DFT calculations show that the chirality is actually imprinted into the molecular electronic system by the surface, i.e., the lowest unoccupied orbital is devoid of mirror symmetry. Our novel reversible spin and hand control scheme can be easily realized at single-molecule level, thus opening up a new avenue to broader applications based on the molecular electronic and spin states.
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Keywords:
- scanning tunneling microscopy /
- metal-phthalocyanine /
- spin state /
- chirality
[1] Aradhya S V, Venkataraman L 2013 Nature Nanotech. 8 399
[2] Bogani L, Wernsdorfer W 2008 Nature Mater. 7 179
[3] Song H, Reed M A, Lee T 2011 Adv. Mater. 23 1583
[4] Binning G, Rohrer H, Gerber C, Weibel E 1982 Phys. Rev. Lett. 49 57
[5] Liao M S, Scheiner S 2001 J. Chem. Phys. 114 9780
[6] Zhao A D, Li Q X, Chen L, Xiang H J, Wang W H, Pan S, Wang B, Xiao X D, Yang J L, Hou J G, Zhu Q S 2005 Science 309 1542
[7] Fu Y S, Ji S H, Chen X, Ma X C, Wu R, Wang C C, Duan W H, Qiu X H, Sun B, Zhang P, Jia J F, Xue Q K 2007 Phys. Rev. Lett. 99 256601
[8] Gao L, Ji W, Hu Y B, Cheng Z H, Deng Z T, Liu Q, Jiang N, Lin X, Guo W, Du S X, Hofer W A, Xie X C, Gao H J 2007 Phys. Rev. Lett. 99 106402
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[10] Liu L W, Yang K, Jiang Y H, Song B Q, Xiao W D, Li L F, Zhou H T, Wang Y L, Du S X, Ouyang M, Hofer W A, Castro Neto A H, Gao H J 2013 Scientific Reports 3 1210
[11] Liu L W, Yang K, Xiao W D, Jiang Y H, Song B Q, Du S X, Gao H J 2013 Appl. Phys. Lett. 103 023110
[12] Yang K, Liu L W, Zhang L Z, Xiao W D, Fei X M, Chen H, Du S X, Ernst K H, Gao H J 2014 ACS Nano 8 2246
[13] Kresse G 1995 Phys. Rev. B 47 558(R)
[14] Kresse G, Joubert D 1999 Phys. Rev. B 59 1758
[15] Barth J V, Brune H, Ertl G, Behm R J 1990 Phys. Rev. B 42 9307
[16] Jiang Y H, Liu L W, Yang K, Xiao W D, Gao H J 2011 Chin. Phys. B 20 096401
[17] Jiang Y H, Xiao W D, Liu L W, Zhang L Z, Lian J C, Yang K, Du S X, Gao H J 2011 J. Phys. Chem. C 115 21750
[18] Mao J H, Zhang H G, Jiang Y H, Pan Y, Gao M, Xiao W D, Gao H J 2009 J. Am. Chem. Soc. 131 14136
[19] Yang K, Xiao W D, Jiang Y H, Zhang H G, Liu L W, Mao J H, Zhou H T, Du S X, Gao H J 2012 J. Phys. Chem. C 116 14052
[20] Mao H K, Hemley R J 1994 Rev. Mod. Phys. 66 671
[21] Gupta J A, Lutz C P, Heinrich A J, Eigler D M 2005 Phys. Rev. B 71 115416
[22] Yang K, Xiao W D, Liu L W, Fei X M, Chen H, Du S X, Gao H J 2014 Nano Research 7 79
[23] Xiao W D, Ruffieux P, Ait-Mansour K, Gröning O, Palotas K, Hofer W A, Gröning P, Fasel R 2006 J. Phys. Chem. B 110 21394
[24] Böhringer M, Morgenstern K, Schneider W D, Whn M, Wöll C, Berndt R 2000 Surf. Sci. 444 199
[25] Cheng Z H, Gao L, Deng Z T, Jiang N, Liu Q, Shi D X, Du S X, Guo H M, Gao H J 2007 J. Phys. Chem. C 111 9240
[26] Fernandez-Torrente I, Monturet S, Franke K J, Fraxedas J, Lorente N, Pascual J I 2007 Phys. Rev. Lett. 99 176103
[27] Fano U 1961 Phys. Rev. 124 1866
[28] Tersoff J, Hamann D R 1983 Phys. Rev. Lett. 50 1998
[29] Hewson A C 1993 The Kondo problem to heavy fermions (Cambridge University Press)
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[1] Aradhya S V, Venkataraman L 2013 Nature Nanotech. 8 399
[2] Bogani L, Wernsdorfer W 2008 Nature Mater. 7 179
[3] Song H, Reed M A, Lee T 2011 Adv. Mater. 23 1583
[4] Binning G, Rohrer H, Gerber C, Weibel E 1982 Phys. Rev. Lett. 49 57
[5] Liao M S, Scheiner S 2001 J. Chem. Phys. 114 9780
[6] Zhao A D, Li Q X, Chen L, Xiang H J, Wang W H, Pan S, Wang B, Xiao X D, Yang J L, Hou J G, Zhu Q S 2005 Science 309 1542
[7] Fu Y S, Ji S H, Chen X, Ma X C, Wu R, Wang C C, Duan W H, Qiu X H, Sun B, Zhang P, Jia J F, Xue Q K 2007 Phys. Rev. Lett. 99 256601
[8] Gao L, Ji W, Hu Y B, Cheng Z H, Deng Z T, Liu Q, Jiang N, Lin X, Guo W, Du S X, Hofer W A, Xie X C, Gao H J 2007 Phys. Rev. Lett. 99 106402
[9] Wang Y F, Kröger J, Berndt R, Hofer W A 2009 J. Am. Chem. Soc. 131 3639
[10] Liu L W, Yang K, Jiang Y H, Song B Q, Xiao W D, Li L F, Zhou H T, Wang Y L, Du S X, Ouyang M, Hofer W A, Castro Neto A H, Gao H J 2013 Scientific Reports 3 1210
[11] Liu L W, Yang K, Xiao W D, Jiang Y H, Song B Q, Du S X, Gao H J 2013 Appl. Phys. Lett. 103 023110
[12] Yang K, Liu L W, Zhang L Z, Xiao W D, Fei X M, Chen H, Du S X, Ernst K H, Gao H J 2014 ACS Nano 8 2246
[13] Kresse G 1995 Phys. Rev. B 47 558(R)
[14] Kresse G, Joubert D 1999 Phys. Rev. B 59 1758
[15] Barth J V, Brune H, Ertl G, Behm R J 1990 Phys. Rev. B 42 9307
[16] Jiang Y H, Liu L W, Yang K, Xiao W D, Gao H J 2011 Chin. Phys. B 20 096401
[17] Jiang Y H, Xiao W D, Liu L W, Zhang L Z, Lian J C, Yang K, Du S X, Gao H J 2011 J. Phys. Chem. C 115 21750
[18] Mao J H, Zhang H G, Jiang Y H, Pan Y, Gao M, Xiao W D, Gao H J 2009 J. Am. Chem. Soc. 131 14136
[19] Yang K, Xiao W D, Jiang Y H, Zhang H G, Liu L W, Mao J H, Zhou H T, Du S X, Gao H J 2012 J. Phys. Chem. C 116 14052
[20] Mao H K, Hemley R J 1994 Rev. Mod. Phys. 66 671
[21] Gupta J A, Lutz C P, Heinrich A J, Eigler D M 2005 Phys. Rev. B 71 115416
[22] Yang K, Xiao W D, Liu L W, Fei X M, Chen H, Du S X, Gao H J 2014 Nano Research 7 79
[23] Xiao W D, Ruffieux P, Ait-Mansour K, Gröning O, Palotas K, Hofer W A, Gröning P, Fasel R 2006 J. Phys. Chem. B 110 21394
[24] Böhringer M, Morgenstern K, Schneider W D, Whn M, Wöll C, Berndt R 2000 Surf. Sci. 444 199
[25] Cheng Z H, Gao L, Deng Z T, Jiang N, Liu Q, Shi D X, Du S X, Guo H M, Gao H J 2007 J. Phys. Chem. C 111 9240
[26] Fernandez-Torrente I, Monturet S, Franke K J, Fraxedas J, Lorente N, Pascual J I 2007 Phys. Rev. Lett. 99 176103
[27] Fano U 1961 Phys. Rev. 124 1866
[28] Tersoff J, Hamann D R 1983 Phys. Rev. Lett. 50 1998
[29] Hewson A C 1993 The Kondo problem to heavy fermions (Cambridge University Press)
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