Rapid Electrochemical Synthesis and Solvatochromic Emission Behavior of Single Crystals of a Heteronuclear Platinum(II)-Copper(I) Complex

Abstract

In this study, we present a novel multicomponent self-assembly approach that offers good potential for crafting heterometallic complexes with exceptional constitutional control. This method generates metal ions from a sacrificial anode by using an electric field, which then coordinates with a metal complex precursor. As a proof-of-concept demonstration, we successfully synthesized single crystals of a heterometallic platinum(II)-copper(I) (Pt[II]-Cu[I]) complex at an exceptionally rapid rate within 30 s by applying a voltage to an acetonitrile solution of [Pt(ppy)(CN)₂]⁻Bu₄N⁺, using copper foil as the anode. Intriguingly, by finely adjusting the intensity and duration of the electric field, we achieved a variety of supramolecular structures, spanning from spherical to rod-like and even flower-like morphologies. Additionally, we found that the photoluminescence property of the resultant crystal can be reversibly shifted among green, orange, and cyan by merely altering the solvent environment. Finally, the crafted heterometallic Pt(II)-Cu(I) complex has shown great promise in advanced anti-counterfeiting applications.

Keywords

anti-counterfeiting / electrochemical synthesis / heterometallic complexes / photoluminescence / solvatochromism

References

[1] S. A. Hua, M. C. Cheng, C. H. Chen, and S. M. Peng, “From Homonuclear Metal String Complexes to Heteronuclear Metal String Complexes,” European Journal of Inorganic Chemistry no. 15 (2015): 2510-2523.

[2] Q. Wang, H. Xiao, Y. Wu, Z. Y. Wang, D. S. Zheng, and Z. N. Chen, “From Homonuclear to Heteronuclear: A Viable Strategy to Promote and Modulate Phosphorescence,” Chemical Communications 56, no. 73 (2020): 10607-10620.

[3] Z. Chen, N. Zhao, Y. Fan, and J. Ni, “Luminescent Groups 10 and 11 Heteropolynuclear Complexes Based on Thiolate or Alkynyl Ligands,” Coordination Chemistry Reviews 253, no. 1-2 (2009): 1-20.

[4] Z. Li, H. Chen, B. Li, et al., “Photoresponsive Luminescent Polymeric Hydrogels for Reversible Information Encryption and Decryption,” Advanced Science 6, no. 21 (2019): 1901529.

[5] S. F. Rice, S. J. Milder, H. B. Gray, R. A. Goldbeck, and D. S. Kliger, “Photophysical Properties of the Lowest Electronic Excited States of Binuclear Rhodium(I) Isocyanide Complexes,” Coordination Chemistry Reviews 43 (1982): 349-354.

[6] V. W. Yam, V. K. Au, and S. Y. Leung, “Light-Emitting Self-Assembled Materials Based on d8 and d10 Transition Metal Complexes,” Chemical Reviews 115, no. 15 (2015): 7589-7728.

[7] Z. Y. Wang, L. Y. Zhang, L. J. Xu, L. X. Shi, J. Y. Wang, and Z. N. Chen, “Elaborate Design of d8-d10 Heteronuclear Phosphors for Ultrahigh-Efficiency Solution-Processed Organic Light-Emitting Diodes,” ACS Applied Materials & Interfaces 13, no. 12 (2021): 14433-14439.

[8] M. W. Cooke and G. S. Hanan, “Luminescent Polynuclear Assemblies,” Chemical Society Reviews 36, no. 9 (2007): 1466-1476.

[9] S. Chakraborty and G. R. Newkome, “Terpyridine-based Metallosupramolecular Constructs: Tailored Monomers to Precise 2D-Motifs and 3D-Metallocages,” Chemical Society Reviews 47, no. 11 (2018): 3991-4016.

[10] J. I. Deneff, K. S. Butler, L. E. S. Rohwer, et al., “Encoding Multilayer Complexity in Anti-Counterfeiting Heterometallic MOF-Based Optical Tags,” Angewandte Chemie International Edition 60, no. 3 (2021): 1203-1211.

[11] Y. Ai, Y. Li, M. H. Chan, G. Xiao, B. Zou, and V. W. W. Yam, “Realization of Distinct Mechano- and Piezochromic Behaviors via Alkoxy Chain Length-Modulated Phosphorescent Properties and Multidimensional Self-Assembly Structures of Dinuclear Platinum(II) Complexes,” Journal of the American Chemical Society 143, no. 28 (2021): 10659-10667.

[12] G. Huang, Y. Jiang, S. Yang, B. S. Li, and B. Z. Tang, “Multistimuli Response and Polymorphism of a Novel Tetraphenylethylene Derivative,” Advanced Functional Materials 29, no. 16 (2019): 1900516.

[13] L. M. C. Luong, M. A. Malwitz, V. Moshayedi, M. M. Olmstead, and A. L. Balch, “Role of Anions and Mixtures of Anions on the Thermochromism, Vapochromism, and Polymorph Formation of Luminescent Crystals of a Single Cation, [(C 6 H 11 NC) 2 Au] +,” Journal of the American Chemical Society 142, no. 12 (2020): 5689-5701.

[14] J. Liu, H. Rijckaert, M. Zeng, et al., “Simultaneously Excited Downshifting/Upconversion Luminescence From Lanthanide-Doped Core/Shell Fluoride Nanoparticles for Multimode Anticounterfeiting,” Advanced Functional Materials 28, no. 17 (2018): 1707365.

[15] A. K. Yetisen, I. Naydenova, F. da Cruz Vasconcellos, J. Blyth, and C. R. Lowe, “Holographic Sensors: Three-Dimensional Analyte-Sensitive Nanostructures and Their Applications,” Chemical Reviews 114, no. 20 (2014): 10654-10696.

[16] X. Yu, H. Zhang, and J. Yu, “Luminescence Anti-Counterfeiting: From Elementary to Advanced,” Aggregate 2, no. 1 (2021): 20-34.

[17] J. Li, K. Chen, J. Wei, et al., “Reversible on-Off Switching of Excitation-Wavelength-Dependent Emission of a Phosphorescent Soft Salt Based on Platinum(II) Complexes,” Journal of the American Chemical Society 143, no. 43 (2021): 18317-18324.

[18] V. A. Milway, F. Tuna, A. R. Farrell, L. E. Sharp, S. Parsons, and M. Murrie, “Directed Synthesis of {Mn 18 Cu 6 } Heterometallic Complexes,” Angewandte Chemie International Edition 52, no. 7 (2013): 1949-1952.

[19] V. W. W. Yam and A. S. Law, “Luminescent d8 Metal Complexes of Platinum(II) and Gold(III): From Photophysics to Photofunctional Materials and Probes,” Coordination Chemistry Reviews 414 (2020): 213298.

[20] K. Chan, C. Y. S. Chung, and V. W. W. Yam, “Parallel Folding Topology-selective Label-free Detection and Monitoring of Conformational and Topological Changes of Different G-quadruplex DNAs by Emission Spectral Changes via FRET of mPPE-Ala-Pt(ii) Complex Ensemble,” Chemical Science 7, no. 4 (2016): 2842-2855.

[21] C. Y. Chung, S. P. Li, K. K. W. Lo, and V. W. W. Yam, “Synthesis and Electrochemical, Photophysical, and Self-Assembly Studies on Water-Soluble pH-Responsive Alkynylplatinum(II) Terpyridine Complexes,” Inorganic Chemistry 55, no. 9 (2016): 4650-4663.

[22] T. R. Cook and P. J. Stang, “Recent Developments in the Preparation and Chemistry of Metallacycles and Metallacages via Coordination,” Chemical Reviews 115, no. 15 (2015): 7001-7045.

[23] Y. Y. Zhang, W. X. Gao, L. Lin, and G. X. Jin, “Recent Advances in the Construction and Applications of Heterometallic Macrocycles and Cages,” Coordination Chemistry Reviews 344 (2017): 323-344.

[24] J. Park, A. N. Pasupathy, J. I. Goldsmith, et al., “Coulomb Blockade and the Kondo Effect in Single-Atom Transistors,” Nature 417, no. 6890 (2002): 722-725.

[25] W. Chen, M. D. Fu, W. H. Tseng, et al., “Conductance and Stochastic Switching of Ligand-Supported Linear Chains of Metal Atoms,” Angewandte Chemie International Edition 45, no. 35 (2006): 5814-5818.

[26] `M. G. Campbell, D. C. Powers, J. Raynaud, et al., “Synthesis and Structure of Solution-Stable One-dimensional Palladium Wires,” Nature Chemistry 3, no. 12 (2011): 949-953.

[27] S. Kundu, S. J. George, and G. U. Kulkarni, “Electric Field Assisted Assembly of 1D Supramolecular Nanofibres for Enhanced Supercapacitive Performance,” Journal of Materials Chemistry A 8, no. 26 (2020): 13106-13113.

[28] Y. Ma, W. Zhao, P. She, et al., “Electric Field Induced Molecular Assemblies Showing Different Nanostructures and Distinct Emission Colors,” Small Methods 3, no. 7 (2019): 1900142.

[29] Z. M. Hudson, C. Sun, K. J. Harris, B. E. Lucier, R. W. Schurko, and S. Wang, “Probing the Structural Origins of Vapochromism of a Triarylboron-Functionalized Platinum(II) Acetylide by Optical and Multinuclear Solid-State NMR Spectroscopy,” Inorganic Chemistry 50, no. 8 (2011): 3447-3457.

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2025 The Author(s). Aggregate published by SCUT, AIEI and John Wiley & Sons Australia, Ltd.