Citation: Lizhu SUN, Jinyun WANG, Zhongning CHEN, Ping DUAN, Qianchong ZHANG. Modulation of charge transport in platinum(Ⅱ) bis(acetylide) complexes by coordination configuration[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(11): 2381-2388. doi: 10.11862/CJIC.20260207 shu

Modulation of charge transport in platinum(Ⅱ) bis(acetylide) complexes by coordination configuration

Lizhu SUN ^{1, 2} ,
Jinyun WANG ¹ ,
Zhongning CHEN ^{1, 2} ,
Ping DUAN ^3,, ,
Qianchong ZHANG ^{1, 2,,}

1.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
College of Chemistry and Chemical Engineering, Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, Guangdong 515063, China

Corresponding author: Ping DUAN, duanping@stu.edu.cn Qianchong ZHANG, zhangqianchong@fjirsm.ac.cn
Received Date: 29 June 2026
Revised Date: 30 September 2026

Figures(4)

Platinum(Ⅱ) bis(acetylide) organometallic complexes exhibit appealing photophysical properties originating from versatile metal-ligand orbital interactions, yet how their coordination geometry governs single-molecule charge transport remains poorly understood. Herein, we have synthesized two geometric isomers, trans-/cis-Pt(PEt₃)₂(C≡CPhSMe)₂ (1-t and 1-c, PhSMe=4-methylthiophenyl), and systematically investigated their single-molecule charge-transport properties by scanning tunneling microscope break junction (STM-BJ) technique and the combination of density functional theory and non-equilibrium Green′s function (DFT-NEGF) calculations. 1-t demonstrated a well-defined conductance peak at 10^-4.5G₀, where G₀ is the quantum conductance (ca. 77 500 nS). In contrast, no detectable conductance signature was recorded for 1-c, whose conductance fell below the instrumental detection limit of 10^-6.0G₀, indicating a more than one-order-of-magnitude conductance suppression. Transition-voltage spectroscopy (TVS) and theoretical studies verify that charge transport in both isomers follows a HOMO-dominated tunneling mechanism and provide a calibrated transmission coefficient (T(E)). Theoretical analyses further reveal two synergistic physical origins for the explicit conductance suppression. First, the bent perpendicular geometry of 1-c induces a severely asymmetric spatial distribution of frontier molecular orbitals over the two acetylide ligands, yielding asymmetric electrode-molecule coupling at two Au—S anchoring interfaces and lowering electron transmission probability. Second, the shortened inter-ligand distance in the cis-configuration not only activates through-space electronic hopping between two acetylide moieties but also results in reverse ring currents localized on the platinum-acetylide structure, which further triggers destructive quantum interference (DQI) and eventually suppresses the conductance in 1-c. By comparison, the linear trans-geometry supports efficient through-bond charge transport with symmetric electrode coupling. This work establishes coordination configuration as an effective structural factor for modulating charge transport characteristics in organometallic molecular wires.
1. [1]
  ZHAO S, YANG Z, JIANG G, HUANG S, BIAN M, LU Y, LIU W. An overview of anticancer platinum N-heterocyclic carbene complexes[J]. Coord. Chem. Rev., 2021, 449: 214217 doi: 10.1016/j.ccr.2021.214217
2. [2]
  COLOMBO A, DRAGONETTI C, GUERCHAIS V, ROBERTO D. An excursion in the second-order nonlinear optical properties of platinum complexes[J]. Coord. Chem. Rev., 2021, 446: 214113 doi: 10.1016/j.ccr.2021.214113
3. [3]
  KALINOWSKI J, FATTORI V, COCCHI M, WILLIAMS J A G. Light-emitting devices based on organometallic platinum complexes as emitters[J]. Coord. Chem. Rev., 2011, 255(21): 2401-2426
4. [4]
  ZHANG Q C, XIAO H, ZHANG X, XU L J, CHEN Z N. Luminescent oligonuclear metal complexes and the use in organic light-emitting diodes[J]. Coord. Chem. Rev., 2019, 378: 121-133 doi: 10.1016/j.ccr.2018.01.017
5. [5]
  YAM V W W. Molecular design of transition metal alkynyl complexes as building blocks for luminescent metal-based materials: Structural and photophysical aspects[J]. Accounts Chem. Res., 2002, 35(7): 555-563 doi: 10.1021/ar0000758
6. [6]
  LEUNG S Y L, LAM W H, ZHU N, YAM V W W. Synthesis, structural characterization, and photophysical study of luminescent face-to-face dinuclear platinum(Ⅱ) alkynyl phosphine complexes and their tetranuclear mixed-metal platinum(Ⅱ)-silver(Ⅰ) and -copper(Ⅰ) complexes[J]. Organometallics, 2010, 29(21): 5558-5569 doi: 10.1021/om100473q
7. [7]
  GAGNON K, ALY S M, BRISACH-WITTMEYER A, BELLOWS D, BERUBE J F, CARON L, ABDELAZIZ A S, FORTIN D, HARVEY P D. Conjugated oligomers and polymers of cis- and trans-platinum(Ⅱ)-para- and ortho-bis(ethynylbenzene)quinone diimine[J]. Organometallics, 2008, 27(10): 2201-2214 doi: 10.1021/om7010563
8. [8]
  COOPER T M, KREIN D M, BURKE A R, MCLEAN D G, ROGERS J E, SLAGLE J E. Asymmetry in platinum acetylide complexes: Confinement of the triplet exciton to the lowest energy ligand[J]. J. Phys. Chem. A, 2006, 110(50): 13370-13378 doi: 10.1021/jp0654516
9. [9]
  SHENG K, WANG Z, LI L, GAO Z Y, TUNG C H, SUN D. Solvent-mediated separation and reversible transformation of 1D supramolecular polymorphs built from [W₁₀O₃₂]₄-templated 48-nuclei silver(Ⅰ) cluster[J]. J. Am. Chem. Soc., 2023, 145(19): 10595-10603 doi: 10.1021/jacs.3c00321
10. [10]
  XU B, TAO N J. Measurement of single-molecule resistance by repeated formation of molecular junctions[J]. Science, 2003, 301(5637): 1221-1223 doi: 10.1126/science.1087481
11. [11]
  VENKATARAMAN L, KLARE J E, NUCKOLLS C, HYBERTSEN M S, STEIGERWALD M L. Dependence of single-molecule junction conductance on molecular conformation[J]. Nature, 2006, 442(7105): 904-907 doi: 10.1038/nature05037
12. [12]
  ALOWAEDI O A, MILAN D C, OERTHEL M C, BOCK S, YUFIT D S, HOWARD J A K, HIGGINS S J, NICHOLS R J, LAMBERT C J, BRYCE M R, LOW P J. Experimental and computational studies of the single-molecule conductance of Ru(Ⅱ) and Pt(Ⅱ) trans-bis(acetylide) complexes[J]. Organometallics, 2016, 35(17): 2944-2954 doi: 10.1021/acs.organomet.6b00472
13. [13]
  DUAN P, LIU J Y, WANG J Y, QU K, CAI S N, WANG F, CHEN L C, HUANG X Y, LI R H, SHI J, ZHANG Q C, HONG W J, CHEN Z N. Enhancing single-molecule conductance of platinum(Ⅱ) complexes through synergistic aromaticity-assisted structural asymmetry[J]. Sci. China Chem., 2020, 63(4): 467-474 doi: 10.1007/s11426-019-9692-3
14. [14]
  DUAN P, LIU J Y, WANG J Y, CHEN L C, WANG F, ZHANG Q C, HONG W J, CHEN Z N. Modulation of the conductance in platinum(Ⅱ) bis(acetylide) molecules through "gating" metal ions[J]. J. Mater. Chem. C, 2019, 7(24): 7259-7266 doi: 10.1039/C9TC02100K
15. [15]
  YAN S S, WANG J Y, PAN Z Y, ZHENG D S, ZHANG Q C, CHEN Z N. Freezing the conductance of platinum(Ⅱ) complexes by quantum interference effect[J]. Chin. Chem. Lett., 2022, 33: 3263-3266 doi: 10.1016/j.cclet.2021.10.092
16. [16]
  MILAN D C, VEZZOLI A, PLANJE I J, LOW P J. Metal bis(acetylide) complex molecular wires: Concepts and design strategies[J]. Dalton Trans., 2018, 47(40): 14125-14138 doi: 10.1039/C8DT02103A
17. [17]
  YANG M, YAN S S, HUANG B, XIANG D, CHEN Z N, CHEN L C, SU K, ZHANG Q C, YUAN D Q. A single-molecule junction based on a covalent organic cage[J]. Angew. Chem.—Int. Edit., 2025, 64(35): e202507894 doi: 10.1002/anie.202507894
18. [18]
  YAN S S, CHEN L C, WANG J Y, DUAN P, PAN Z Y, QU K, HONG W J, CHEN Z N, ZHANG Q C. Exploring a linear combination feature for predicting the conductance of parallel molecular circuits[J]. Nano Lett., 2023, 23(20): 9399-9405 doi: 10.1021/acs.nanolett.3c02763
19. [19]
  LAMBERT C J. Basic concepts of quantum interference and electron transport in single-molecule electronics[J]. Chem. Soc. Rev., 2015, 44(4): 875-888 doi: 10.1039/C4CS00203B
20. [20]
  LIU J Y, HUANG X Y, WANG F, HONG W J. Quantum interference effects in charge transport through single-molecule junctions: Detection, manipulation, and application[J]. Accounts Chem. Res., 2019, 52(1): 151-160 doi: 10.1021/acs.accounts.8b00429
21. [21]
  SOLOMON G C, HERRMANN C, HANSEN T, MUJICA V, RATNER M A. Exploring local currents in molecular junctions[J]. Nat. Chem., 2010, 2(3): 223-228 doi: 10.1038/nchem.546
22. [22]
  SONOGASHIRA K, TOHDA Y, HAGIHARA N. Convenient synthesis of acetylenes—Catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes, and bromopyridines[J]. Tetrahedron Lett., 1975, 16(50): 4467-4470 doi: 10.1016/S0040-4039(00)91094-3
23. [23]
  PAN Z C, DONG G, SHANG C, LI R H, GAO T Y, LIN L C, DUAN H, LI X H, BAI J, LAI Y L, WU W F, SHI J, LIU J Y, HONG W J. XMe—Xiamen molecular electronics code: An intelligent and open-source data analysis tool for single-molecule conductance measurements[J]. Chin. J. Chem., 2023, 42(3): 317-329
24. [24]
  LIU J Y, ZHAO X T, ZHENG J T, HUANG X Y, TANG Y X, WANG F, LI R H, PI J C, HUANG C C, WANG L, YANG Y, SHI J, MAO B W, TIAN Z Q, BRYCE M R, HONG W J. Transition from tunneling leakage current to molecular tunneling in single-molecule junctions[J]. Chem, 2019, 5(2): 390-401 doi: 10.1016/j.chempr.2018.11.002
25. [25]
  BAI J, DAAOUB A, SANGTARASH S, LI X, TANG Y, ZOU Q, SADEGHI H, LIU S Y, HUANG X, TAN Z, LIU J, YANG Y, SHI J, MÉSZÁROS G, CHEN W, LAMBERT C, HONG W J. Anti-resonance features of destructive quantum interference in single-molecule thiophene junctions achieved by electrochemical gating[J]. Nat. Mater., 2019, 18(4): 364-369 doi: 10.1038/s41563-018-0265-4
26. [26]
  HUANG C, RUDNEV A V, HONG W J, WANDLOWSKI T. Break junction under electrochemical gating: Testbed for single-molecule electronics[J]. Chem. Soc. Rev., 2015, 44(4): 889-901 doi: 10.1039/C4CS00242C
27. [27]
  KAMENETSKA M, KOENTOPP M, WHALLEY A C, PARK Y S, STEIGERWALD M L, NUCKOLLS C, HYBERTSEN M S, VENKATARAMAN L. Formation and evolution of single-molecule junctions[J]. Phys. Rev. Lett., 2009, 102(12): 126803 doi: 10.1103/PhysRevLett.102.126803
28. [28]
  FRISENDA R, JANSSEN V A E C, GROZEMA F C, van der ZANT H S J, RENAUD N. Mechanically controlled quantum interference in individual π-stacked dimers[J]. Nat. Chem., 2016, 8(12): 1099-1104 doi: 10.1038/nchem.2588
29. [29]
  FRISCH M J, TRUCKS G W, SCHLEGEL H B, SCUSERIA G E, ROBB M A, CHEESEMAN J R, SCALMANI G, BARONE V, MENNUCCI B, PETERSSON G A, NAKAJIMA H, CARICATO M, LI X, HRATCHIAN H P, IZMAYLOV A F, BLOINO J, ZHENG G, SONNENBERG J L, HADA M, EHARA M, TOYOTA K, FUKUDA R, HASEGAWA J, ISHIDA M, NAKAJIMA T, HONDA Y, KITAO O, NAKAI H, VREVEN T, MONTGOMERY J A, PERALTA J J E, OGLIARO F, BEARPARK M, HEYD J J, BROTHERS E, KUDIN K N, STAROVEROV V N, KEITH T, KOBAYASHI R, NORMAND J, RAGHAVACHARI K, RENDELL A, BURANT J C, IYENGAR S S, TOMASI J, COSSI M, REGA N, MILLAM J M, KLENE M, KNOX J E, CROSS J B, BAKKEN V, ADAMO C, JARAMILLO J, GOMPERTS R, STRATMANN R E, YAZYEV O, AUSTIN A J, CAMMI R, POMELLI C, OCHTERSKI J W, MARTIN R L, MOROKUMA K, ZAKRZEWSKI V G, VOTH G A, SALVADOR P, FOX J J, Gaussian09, Revision D. 01[CP], Wallingford CT: Gaussian, Inc., 2013.
30. [30]
  XIE Z, BÂLDEA I, FRISBIE C D. Determination of energy-level alignment in molecular tunnel junctions by transport and spectroscopy: Self-consistency for the case of oligophenylene thiols and dithiols on Ag, Au, and Pt electrodes[J]. J. Am. Chem. Soc., 2019, 141(8): 3670-3681 doi: 10.1021/jacs.8b13370
31. [31]
  XIE Z, BÂLDEA I, FRISBIE C D. Energy level alignment in molecular tunnel junctions by transport and spectroscopy: Self-consistency for the case of alkyl thiols and dithiols on Ag, Au, and Pt electrodes[J]. J. Am. Chem. Soc., 2019, 141(45): 18182-18192 doi: 10.1021/jacs.9b08905
32. [32]
  GARNER M H, LI H, CHEN Y, SU T A, SHANGGUAN Z, PALEY D W, LIU T, NG F, LI H, XIAO S, NUCKOLLS C, VENKATARAMAN L, SOLOMON G C. Comprehensive suppression of single-molecule conductance using destructive σ-interference[J]. Nature, 2018, 558(7710): 415-419 doi: 10.1038/s41586-018-0197-9
33. [33]
  WU S D, LIU S T, CAI Z M, SUN B, LIU X D, SHI L Y Y, LAMBERT C J, ZHANG H L. Breaking interference-driven reversal currents to boost single-molecule conductance[J]. Angew. Chem.—Int. Edit., 2025, 64(50): e202520318 doi: 10.1002/anie.202520318
1. [1]
  Jingwen Wang , Minghao Wu , Xing Zuo , Yaofeng Yuan , Yahao Wang , Xiaoshun Zhou , Jianfeng Yan . Advances in the Application of Electrochemical Regulation in Investigating the Electron Transport Properties of Single-Molecule Junctions. University Chemistry, 2025, 40(3): 291-301. doi: 10.12461/PKU.DXHX202406023
2. [2]
  Yuejiao An , Wenxuan Liu , Yanfeng Zhang , Jianjun Zhang , Zhansheng Lu . Revealing Photoinduced Charge Transfer Mechanism of SnO₂/BiOBr S-Scheme Heterostructure for CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(12): 2407021-0. doi: 10.3866/PKU.WHXB202407021
3. [3]
  Wenke ZHENG , Ce LIU , Wei CHEN , Hongshan KE , Fanlong ZENG , Yibo LEI , Anyang LI , Wenyuan WANG . Synthesis and bonding analysis of low-coordinate Fe and Cr complexes with ultra-bulky silylamino groups. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1285-1293. doi: 10.11862/CJIC.20250095
4. [4]
  Zhenzhen Xue , Lixing Zhao , Jie Pan , Jixiang Hu . 配位化合物教学中的教研结合探索. University Chemistry, 2026, 41(9): 101-106. doi: 10.12461/PKU.DXHX202509020
5. [5]
  Shunping WANG , Chuandong GE , Shuguang QU , Tianduo LI , Shaomin WANG , Qingyuan YANG . Synthesis of a fluorescent probe based on urea-based coordination and Si—O bond cleavage for F^- and Cr(Ⅵ) detection. Chinese Journal of Inorganic Chemistry, 2026, 42(2): 297-308. doi: 10.11862/CJIC.20250214
6. [6]
  Xuqiang Hao , Yuanjin He , Xue Wang , Yuqiang Hao , Zhiliang Jin . Co-doping-induced asymmetric charge distribution in S-scheme CoCdS/graphdiyne heterojunction for broad-spectrum photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2026, 42(11): 100376-0. doi: 10.1016/j.actphy.2026.100376
7. [7]
  Dan Zhou , Xinyue Liu , Zijing Guo , Jianping Yang , Zeying Guo , Zhuoer Ren , E Yu , Ting Pan , Doudou Ren , Zhicong Zeng . Development and teaching design of astigmatic displacement microscopy: a recommended experiment for chemical metrology (micro-nano advanced characterization). University Chemistry, 2026, 41(6): 196-203. doi: 10.12461/PKU.DXHX202511180
8. [8]
  Yinglong WANG , Jinlin ZHAI , Jianjie XU , Xinyuan XIE , Sijie FAN , Qionghua JIN , Hongliang HAN , Zhongfeng LI . Synthesis and structural characterization of Cu(Ⅰ) complexes containing a bridging nitrogen ligand with a double bond and a diphosphine ligand. Chinese Journal of Inorganic Chemistry, 2026, 42(11): 2420-2428. doi: 10.11862/CJIC.20260235
9. [9]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
10. [10]
  Ming Li , Zhaoyin Li , Mengzhu Liu , Shaoxiang Luo . Unveiling the Artistry of Mordant Dyeing: The Coordination Chemistry Beneath. University Chemistry, 2024, 39(5): 258-265. doi: 10.3866/PKU.DXHX202311085
11. [11]
  Quanguo Zhai , Peng Zhang , Wenyu Yuan , Ying Wang , Shu'ni Li , Mancheng Hu , Shengli Gao . Reconstructing the “Fundamentals of Coordination Chemistry” in Inorganic Chemistry Course. University Chemistry, 2024, 39(11): 117-130. doi: 10.12461/PKU.DXHX202403065
12. [12]
  Wen Jiang , Jieli Lin , Zhongshu Li . 低配位含磷官能团的研究进展. University Chemistry, 2025, 40(8): 138-151. doi: 10.12461/PKU.DXHX202409144
13. [13]
  Chunmei GUO , Weihan YIN , Jingyi SHI , Jianhang ZHAO , Ying CHEN , Quli FAN . Facile construction and peroxidase-like activity of single-atom platinum nanozyme. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1633-1639. doi: 10.11862/CJIC.20240162
14. [14]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
15. [15]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . Efficient Photocatalytic Production of H₂O₂ over ZnO/D-A Conjugated Polymer S-scheme Heterojunction and Charge Transfer Dynamics Investigation. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-0. doi: 10.3866/PKU.WHXB202406027
16. [16]
  Chengtian Liang , Boyuan Zheng , Ning Fang . 第38届中国化学奥林匹克(初赛)配位化学试题解析. University Chemistry, 2025, 40(8): 394-400. doi: 10.12461/PKU.DXHX202410054
17. [17]
  Huifang XIAO , Xiaoqian HU , Xiaofan YE , Lihui LIU , Fen NIE , Yanrong DING , Ying MA , Yanzhu LIU , Yongxiu LI . Coordination-enhanced leaching of bastnaesite from mixed rare earth concentrates and comprehensive recycling of valuable elements. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 141-151. doi: 10.11862/CJIC.20250049
18. [18]
  Hequn Yang , Fei Rao , Dean Pan , Liu Chen , Numan Abbas , Gangqiang Zhu . Rare earth praseodymium single atoms on g-C₃N₄ tubes for enhanced in-plane charge transfer towards H₂O₂ production in pure water. Acta Physico-Chimica Sinica, 2026, 42(6): 100210-0. doi: 10.1016/j.actphy.2025.100210
19. [19]
  Ruiying WANG , Hui WANG , Fenglan CHAI , Zhinan ZUO , Benlai WU . Three-dimensional homochiral Eu(Ⅲ) coordination polymer and its amino acid configuration recognition. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 877-884. doi: 10.11862/CJIC.20250052
20. [20]
  Zhi Zhou , Yu-E Lian , Yuqing Li , Hui Gao , Wei Yi . New Insights into the Molecular Mechanism Behind Clinical Tragedies of “Cephalosporin with Alcohol”. University Chemistry, 2025, 40(3): 42-51. doi: 10.12461/PKU.DXHX202403104

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(87)
HTML views(6)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142