Cu(I)/Cu(II) Creutz–Taube Mixed‐Valence 2D Coordination Polymers

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Cu(I)/Cu(II) Creutz–Taube Mixed‐Valence 2D Coordination Polymers
Title:
Cu(I)/Cu(II) Creutz–Taube Mixed‐Valence 2D Coordination Polymers
Journal Title:
Small Methods
Keywords:
Publication Date:
22 December 2022
Citation:
Li, N., Wu, G., Xi, S., Wei, F., Lin, M., Qiu, J., Zheng, J., Yi, J., Seng, D. H. L., Lee, C. J. J., Repaka, D. V. M., Liu, X., Wong, Z. M., Zhu, Q., Yang, S., & Luo, H. (2022). Cu(I)/Cu(II) Creutz–Taube Mixed‐Valence 2D Coordination Polymers. Small Methods, 7(1). Portico. https://doi.org/10.1002/smtd.202201166
Abstract:
AbstractGraphene‐like 2D coordination polymers (GCPs) have been of central research interest in recent decades with significant impact in many fields. According to classical coordination chemistry, Cu(II) can adopt the dsp2 hybridization to form square planar coordination geometry, but not Cu(I); this is why so far, there has been few 2D layered structures synthesized from Cu(I) precursors. Herein a pair of isostructural GCPs synthesized by the coordination of benzenehexathiol (BHT) ligands with Cu(I) and Cu(II) ions, respectively, is reported. Spectroscopic characterizations indicate that Cu(I) and Cu(II) coexist with a near 1:1 ratio in both GCPs but remain indistinguishable with a fractional oxidation state of +1.5 on average, making these two GCPs a unique pair of Creutz–Taube mixed‐valence 2D structures. Based on density functional theory calculations, an intramolecular pseudo‐redox mechanism is further uncovered whereby the radicals on BHT ligands can oxidize Cu(I) or reduce Cu(II) ions upon coordination, thus producing isostructures with distinct electron configurations. For the first time, it is demonstrated that using Cu(I) or Cu(II), one can achieve 2D isostructures, indicating an unusual fact that a neutral periodic structure can host a different number of total electrons as ground states, which may open a new chapter for 2D materials.
License type:
Publisher Copyright
Funding Info:
This research / project is supported by the A*STAR - AME Young Individual Research Grant
Grant Reference no. : A2084c0174

This research / project is supported by the A*STAR - IMRE
Grant Reference no. : SC25/21-102319

This research / project is supported by the A*STAR - SERC
Grant Reference no. : 1527200020, 1527200024, A1898b0043
Description:
This is the peer reviewed version of the following article: Li, N., Wu, G., Xi, S., Wei, F., Lin, M., Qiu, J., Zheng, J., Yi, J., Seng, D. H. L., Lee, C. J. J., Repaka, D. V. M., Liu, X., Wong, Z. M., Zhu, Q., Yang, S., & Luo, H. (2022). Cu(I)/Cu(II) Creutz–Taube Mixed‐Valence 2D Coordination Polymers. Small Methods, 7(1). Portico. https://doi.org/10.1002/smtd.202201166, which has been published in final form at doi.org/10.1002/smtd.202201166. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
ISSN:
2366-9608
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