Luminescence Enhancement of an Indium(III) Complex Through Introducing an Electron-Donating Group in (1H-Pyrazol-1-yl)pyridazine
New deep-blue-emitting materials are crucial for Organic Light-Emitting Diode (OLED) technology, as iridium-based blue emitters often suffer from degradation and inadequate colour purity. Indium(III) complexes offer an alternative, since the d10 configuration of In3+ precludes metal-centred transitions, and emission arises from ligand-centred states via the chelation-enhanced fluorescence (CHEF) effect. We previously reported complexes 1 ([In(LH)(H2O)Cl3]) and 2 ([In(LMe)2Cl2][InCl4]), which exhibited excitation-dependent emission, and the electronic transitions were assigned as ILCT for 1 and mixed ILCT/LL’CT for 2. Herein, we present a new complex, complex 3, i.e., [In(LMorph)2Cl2][InCl4], where LMorph contains electron-donating morpholine substituents, in contrast to the acceptor chloride group in LH and LMe. Complex 3 was characterised by elemental CHN analysis, infrared spectroscopy (IR), nuclear magnetic resonance spectroscopy (NMR), ultraviolet–visible spectroscopy (UV-Vis), single-crystal X-ray diffraction analysis (SC-XRD), and photoluminescence. The ionic structure of 3 is analogous to 2, with a cis-octahedral [In(LMorph)2Cl2]+ cation and tetrahedral [InCl4]− anion. The UV-Vis spectrum of 3 shows a significant bathochromic shift relative to 1 and 2 which is attributable to the morpholine group. TD-DFT calculations were employed to assign the electronic transitions. The introduction of a morpholino group into the pyridazine ring resulted in significant changes to the solid-state photoluminescence properties of the indium complex: (i) the emission maximum shifted to the red region (CIE 1931 coordinates: 0.1725, 0.2487), (ii) the lifetime increased by an order of magnitude, and (iii) the quantum yield rose to 15%. This work highlights that substituent variation on the pyrazolyl–pyridazine scaffold provides a versatile route to tune the structural and photophysical properties of indium(III) complexes.
Authors
- Elvira I. Musina (ORCID: https://orcid.org/0000-0003-3187-8652)
- Евгения Сергеевна Седых
- N. F. Romashev (ORCID: https://orcid.org/0000-0002-5711-1882)
- Yulia S. Spiridonova (ORCID: https://orcid.org/0000-0002-6673-327X)
- Katerina A. Vinogradova (ORCID: https://orcid.org/0000-0002-2163-530X)
- Artem L. Gushchin (ORCID: https://orcid.org/0000-0003-3214-1433)
- Alexey Yuryevich Vorob’ev
- Veronika Igorevna Komlyagina
- Iakov Sergeevich Fomenko
- Marat Damirovich Nafikov
- Marianna Ivanovna Rakhmanova
- Nikita Vasilievich Naletov
Institutions
- Novosibirsk State University (RU)
- Novosibirsk Institute of Organic Chemistry (RU)
- A.E. Arbuzov Institute of Organic and Physical Chemistry (RU)
- Nikolaev Institute of Inorganic Chemistry (RU)
Publication Details
- Journal
- Molecules
- Published
- 2026-09-11
- DOI
- https://doi.org/10.3390/molecules31183217
- Primary Topic
- Organic Light-Emitting Diodes Research
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Russian Science Foundation