Issue 21, 2018

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

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

Supplementary files

Article information

Article type
Paper
Submitted
17 Mar 2018
Accepted
01 May 2018
First published
02 May 2018

Dalton Trans., 2018,47, 7306-7315

“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, 47, 7306 DOI: 10.1039/C8DT01041B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements