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“Two-in-one” organic–inorganic hybrid MnII complexes exhibiting dual-emissive phosphorescence

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Abstract

Unprecedented organic–inorganic hybrid complexes, [Mn(L)3]MnHal4, containing both four- and hexacoordinated Mn2+ ions were synthesized by reacting MnCl2 or MnBr2 with bis(phosphine oxide) ligands (L) such as dppmO2, dppeO2, and 2,3-bis(diphenylphosphinyl)-1,3-butadiene (dppbO2). In the [Mn(L)3]2+ cation of the complexes, the Mn2+ ion features a [MnO6] octahedral coordination environment (Oh), and the [MnHal4]2− anion adopts a tetrahedral geometry (Td). These “two-in-one” complexes exhibit strong long-lived luminescence (τav = 12–15 ms at 300 K) having interesting thermochromic behavior attributed to the thermal equilibrium between two emission bands. So, in an emission spectrum of the typical complex [Mn(dppbO2)3]MnBr4, the intense “red” (ca. 620 nm) and weak “green” (ca. 520 nm) bands, originating from Mn2+ ions in Oh and Td environments, respectively, are observed. Cooling from 300 to 77 K simultaneously leads to (i) redshift of both bands by ca. 20 nm, (ii) increasing their intensities, and (iii) causing a substantial change of their integral intensity ratio from about 4 : 1 to 2 : 1. As a result, the colour of the emission changes from orange (CIE 0.56, 0.45) at 300 K to deep red (CIE 0.62, 0.39) at 77 K. This behavior was rationalized using steady-state and time-resolved fluorescent spectroscopy at various temperatures. The high photoluminescence quantum yields (up to 61% at 300 K) and fascinating dual-emissive phosphorescence coupled with high thermal stability and solubility suggest a high potential of this novel class of emissive Mn2+ complexes as promising emitters for OLED devices and potential stimuli-responsive materials.

Graphical abstract: “Two-in-one” organic–inorganic hybrid MnII complexes exhibiting dual-emissive phosphorescence

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Publication details

The article was received on 17 Mar 2018, accepted on 01 May 2018 and first published on 02 May 2018


Article type: Paper
DOI: 10.1039/C8DT01041B
Citation: Dalton Trans., 2018, Advance Article
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    “Two-in-one” organic–inorganic hybrid MnII complexes exhibiting dual-emissive phosphorescence

    A. S. Berezin, D. G. Samsonenko, V. K. Brel and A. V. Artem'ev, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT01041B

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