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Issue 24, 2019
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Modulation of the conductance in platinum(ii) bis(acetylide) molecules through “gating” metal ions

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Abstract

Mononuclear platinum(II) complex trans-Pt(PPh3)2(C[triple bond, length as m-dash]CC6H4SMe-4)2 (1-Pt) and its derivatives [PtM(dppm)2(C[triple bond, length as m-dash]CC6H4SMe-4)2]+ (dppm = bis(diphenylphosphino)methane; M = Au, 2-PtAu; Ag, 2-PtAg; Cu, 2-PtCu) with “mono-gating” metal ions and [PtM2(dpmp)2(C[triple bond, length as m-dash]CC6H4SMe-4)2]2+ (dppm = bis(diphenylphosphinomethyl)phenylphosphine; M = Au, 3-PtAu2; Ag, 3-PtAg2) with “dual-gating” metal ions were elaborately designed to modulate the conductance in platinum(II) bis(σ-acetylide) complexes through “gating” d10 metal ions. The single-molecule conductance measurements by the STM-BJ technique demonstrate that the conductance follows 10−4.5 (1-Pt) > 10−4.8 (2-PtAu) > 10−4.9 (2-PtAg) > 10−5.0 (2-PtCu) > 10−5.1 (3-PtAu2) > 10−5.3 (3-PtAg2) G0. Undoubtedly, charge transport along the platinum(II) bis(σ-acetylide) backbone is progressively restricted by introducing one to two “gating” M ions to the mononuclear platinum(II) molecule. As revealed by X-ray crystallography, the “gating” d10 metal ion is substantially bound to the acetylide and in fact the M–acetylide bonding is progressively enhanced in the order Au–Cacetylide → Ag–Cacetylide → Cu–Cacetylide, which coincides with a progressive decrease in the conductance as 10−4.8 (2-PtAu) > 10−4.9 (2-PtAg) > 10−5.0 (2-PtCu) G0. The M–acetylide coordination blocks the charge transport along the platinum(II) bis(σ-acetylide) backbone so that the d10 metal ion behaves as a resistor to suppress the conductance. Theoretical studies confirm that the “gating” metal ions control the HOMO energy, which is lowered by the increased d orbital contribution of “gating” metal ions through Pt–M interactions.

Graphical abstract: Modulation of the conductance in platinum(ii) bis(acetylide) molecules through “gating” metal ions

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Supplementary files

Article information


Submitted
19 Apr 2019
Accepted
09 May 2019
First published
09 May 2019

J. Mater. Chem. C, 2019,7, 7259-7266
Article type
Paper

Modulation of the conductance in platinum(II) bis(acetylide) molecules through “gating” metal ions

P. Duan, J. Liu, J. Wang, L. Chen, F. Wang, Q. Zhang, W. Hong and Z. Chen, J. Mater. Chem. C, 2019, 7, 7259
DOI: 10.1039/C9TC02100K

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