Wydział Chemii

Sabina W. Jaros

Jerzy Sokolnicki

Miłosz Siczek

Piotr Smoleński

2023

Inorganic Chemistry

62

19898-19907

10.1021/acs.inorgchem.3c01908

Naukowa

Angielski

Artykuł

The new series of copper(I) coordination polymers [Cu(N–N)(μ-PTA)]_n[PF₆]_n {N–N = dmbpy (1), bpy (2), ncup (3), and phen (4)} were generated by straightforward reaction in solution or through a mechanochemical route, of [Cu(MeCN)₄][PF₆] with 1,3,5-triaza-7-phosphaadamantane (PTA) and the corresponding polypyridines, namely, 5,5′-dimethyl-2,2′-bipyridine (dmbpy), 2,2′-bipyridine (bpy), 2,9-dimethyl-1,10-phenanthroline (ncup), and 1,10-phenanthroline (phen). The compounds were obtained as air-stable solids and fully characterized by IR, NMR spectroscopy, and elemental analyses. The molecular structures were confirmed by single-crystal X-ray diffraction analysis (for 1, 2, and 4), revealing infinite one-dimensional (1D) linear chains driven by μ-PTA N,P-linkers. All tested Cu(I) polymeric compounds show emission at room temperature, which was attributed to thermally activated delayed fluorescence (TADF). Evidence of the involvement of the excited singlet state in the emission process is presented. Comparing the photophysical properties of 1 and 2 as well as 3 and 4, of which 1 and 3 have a stiffened structure, by introducing a methyl group to one of the ligands, we demonstrate how TADF properties depend on molecular rigidity. It is shown that stiffening of the structure reduces the flattening distortion around the Cu(I) center in the ³MLCT state. As a result, the ΔE(S₁–T₁) energy gap becomes smaller and the fluorescence quantum yield increases without significantly extending the emission lifetime. In particular, the ΔE(S₁–T₁) values for complexes 1 and 3 are among the shortest reported in the scientific literature, 253 and 337 cm^–1, and the TADF lifetimes are τ(300 K) = 5.7 and 4.2 μs, respectively. The fluorescence quantum yields for these complexes are measured to be Φ_PL(300 K) = 70 and 80%.

Coordination polymers, Crystals, Fluorescence, Ligands, Luminescence

CC-BY

http://dx.doi.org/10.1021/acs.inorgchem.3c01908

https://www.acs.org/content/acs/en.html