The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes

Paderina, Aleksandra; Melnikov, Alexey; Slavova, Sofia; Sizov, Vladimir; Gurzhiy, Vladislav; Petrovskii, Stanislav; Luginin, Maksim; Levin, Oleg; Koshevoy, Igor; Grachova, Elena

doi:10.3390/molecules27072250

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The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes

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Institute of Chemistry, St. Petersburg University, Universitetskii pr. 26, 198504 St. Petersburg, Russia

Centre for Nano- and Biotechnologies, Peter the Great St. Petersburg Polytechnic University, 195251 St. Petersburg, Russia

Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria

⁴

Institute of Earth Sciences, St. Petersburg University, 199034 St. Petersburg, Russia

⁵

Department of Chemistry, University of Eastern Finland, 80101 Joensuu, Finland

Author to whom correspondence should be addressed.

Academic Editor: Huimin Guo

Molecules 2022, 27(7), 2250; https://doi.org/10.3390/molecules27072250

Received: 22 February 2022 / Revised: 26 March 2022 / Accepted: 28 March 2022 / Published: 30 March 2022

(This article belongs to the Special Issue Synthesis and Photophysical Properties of Transition Metal Complexes)

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Abstract

In this work we show, using the example of a series of [Cu(Xantphos)(N^N)]⁺ complexes (N^N being substituted 5-phenyl-bipyridine) with different peripheral N^N ligands, that substituents distant from the main action zone can have a significant effect on the physicochemical properties of the system. By using the C≡C bond on the periphery of the coordination environment, three hybrid molecular systems with −Si(CH₃)₃, −Au(PR₃), and −C₂HN₃(CH₂)C₁₀H₇ fragments were produced. The Cu(I) complexes thus obtained demonstrate complicated emission behaviour, which was investigated by spectroscopic, electrochemical, and computational methods in order to understand the mechanism of energy transfer. It was found that the −Si(CH₃)₃ fragment connected to the peripheral C≡C bond changes luminescence to long-lived intra-ligand phosphorescence, in contrast to MLCT phosphorescence or TADF. The obtained results can be used for the design of new materials based on Cu(I) complexes with controlled optoelectronic properties on the molecular level, as well as for the production of hybrid systems. View Full-Text

Keywords: copper(I) complex; bipyridine derivative; luminescence; quantum chemical calculation

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Paderina, A.; Melnikov, A.; Slavova, S.; Sizov, V.; Gurzhiy, V.; Petrovskii, S.; Luginin, M.; Levin, O.; Koshevoy, I.; Grachova, E. The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes. Molecules 2022, 27, 2250. https://doi.org/10.3390/molecules27072250

AMA Style

Paderina A, Melnikov A, Slavova S, Sizov V, Gurzhiy V, Petrovskii S, Luginin M, Levin O, Koshevoy I, Grachova E. The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes. Molecules. 2022; 27(7):2250. https://doi.org/10.3390/molecules27072250

Chicago/Turabian Style

Paderina, Aleksandra, Alexey Melnikov, Sofia Slavova, Vladimir Sizov, Vladislav Gurzhiy, Stanislav Petrovskii, Maksim Luginin, Oleg Levin, Igor Koshevoy, and Elena Grachova. 2022. "The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes" Molecules 27, no. 7: 2250. https://doi.org/10.3390/molecules27072250

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The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes

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