"Two-in-one" organic-inorganic hybrid MnII complexes exhibiting dual-emissive phosphorescence

Unprecedented organic-inorganic hybrid complexes, [Mn(L)(3)]MnHal(4), containing both four- and hexacoordinated Mn2+ ions were synthesized by reacting MnCl2 or MnBr2 with bis(phosphine oxide) ligands (L) such as dppmO(2), dppeO(2), and 2,3-bis(diphenylphosphinyl)-1,3-butadiene (dppbO(2)). In the [Mn(L)(3)](2+) cation of the complexes, the Mn2+ ion features a [MnO6] octahedral coordination environment (O-h), and the [MnHal(4)](2-) anion adopts a tetrahedral geometry (T-d). These two-in-one complexes exhibit strong long-lived luminescence ((av) = 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(dppbO(2))(3)]MnBr4, the intense red (ca. 620 nm) and weak green (ca. 520 nm) bands, originating from Mn2+ ions in O-h and T-d 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.