Issue 11, 2024

Cyanido-bridged diplatinum(ii) complexes: ligand and solvent effect on aggregation and luminescence

Abstract

The association of platinum(II)-based luminophores, which is caused by metal⋯metal and π–π stacking interactions, has been actively exploited in supramolecular construction of photofunctional molecular materials. Herein, we describe a series of bimetallic complexes [{Pt(C^N^/*N)}2(CN)][BAr4F], containing cyanido-bridged cyclometalated Pt(II) chromophore fragments (HC^N^N = 6-phenyl-2,2′-bipyridine, (benzyltriazolyl)-phenylpyridine, and pyrazolyl-phenylpyridine; HC^N*N = N-pentyl-6-phenyl-N-(pyridin-2-yl)pyridin-2-amine; ^/* denote five/six-membered metallocycles). These compounds are intensely phosphorescent at room temperature showing quantum yields up to 0.73 in solution and 0.62 in the solid state, which are generally higher than those of the mononuclear relatives [Pt(C^N^/*N)(CN)]. The complex cations bearing sterically unhindered C^N^N ligands readily assemble in solution, reaching the tetrameric species [{Pt(C^N^N)}2(CN)]44+ as suggested by diffusion NMR spectroscopy. The size of the aggregates can be regulated by the concentration, temperature, and polarity of the solvent that allows to alter the emission from green to near-IR. In the solid state, the maximum of low-energy luminescence is shifted up to 912 nm. The results show that photophysical properties of discrete complexes and the intermolecular aggregation can be substantially enhanced by utilizing the rigid bimetallic units giving rise to novel dynamic light emitting Pt(II) systems.

Graphical abstract: Cyanido-bridged diplatinum(ii) complexes: ligand and solvent effect on aggregation and luminescence

Supplementary files

Transparent peer review

To support increased transparency, we offer authors the option to publish the peer review history alongside their article.

View this article’s peer review history

Article information

Article type
Edge Article
Submitted
25 dec 2023
Accepted
23 jan 2024
First published
12 feb 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 4005-4018

Cyanido-bridged diplatinum(II) complexes: ligand and solvent effect on aggregation and luminescence

V. V. Khistiaeva, S. Buss, T. Eskelinen, P. Hirva, N. Kinnunen, J. Friedel, L. Kletsch, A. Klein, C. A. Strassert and I. O. Koshevoy, Chem. Sci., 2024, 15, 4005 DOI: 10.1039/D3SC06941A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements