Luminescence of the Mn2+ ion in non-Oh and Td coordination environments: the missing case of square pyramid

Artem’ev, Alexander V.; Davydova, Maria P.; Berezin, Alexey S.; Brel, V. K.; Morgalyuk, V. P.; Bagryanskaya, I. Yu.; Samsonenko, Denis G.

doi:10.1039/c9dt03283e

Cited by 48 publications

(14 citation statements)

References 52 publications

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“…However, despite the low quantum efficiency ( Φ PL of 4 – 6 are 1 %, 2 % and 1 %, respectively), complexes 4 and 6 are characterized by a unique multicolor emission expressed by two complementing bands, the ratio of which is sensitive to the excitation wavelength. It is relevant to note in this regard that the Mn‐based multicolor emitting materials are still very limited,, although they are high‐demand for the creation of low‐cost white OLEDs of next generation as well as new photoswitches and sensing devices.…”

Section: Resultsmentioning

confidence: 99%

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Manganese(II) Thiocyanate Complexes with Bis(phosphine Oxide) Ligands: Synthesis and Excitation Wavelength‐Dependent Multicolor Luminescence

et al. 2020

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First examples of luminescent MnII thiocyanate complexes are presented. A series of such compounds has been synthesized via the reaction of Mn(NCS)2 with bis(phosphine oxides), Ph2P(O)–X–(O)PPh2, where X = CH2 (L1), CH2CH2 (L2), CH2CH2CH2 (L3), CH2C(=CH2)CH2 (L4), C(=CH2)C(=CH2) (L5) and C≡C (L6). The L1, L3 and L4 ligands, when reacted with Mn(NCS)2 on air (EtOH/acetone, r.t.), produce chelate complexes [MnII(O^O)2(NCS)2]. Under similar conditions, L5 gives ionic complex [MnII(L5)3][MnII(NCS)4], whereas L6 affords chain coordination polymer (CP) [MnII(L6)2(NCS)2]n. By contrast, ligand L2 results in formation of mixed‐valent chain CP [MnIIMnIII(L2)3(NCS)5]n. Complex [Mn(L4)2(NCS)2] and CP [Mn(L6)2(NCS)2]n display unique dual luminescence, i.e. the intraligand fluorescence (blue band) and MnII‐centered phosphorescence (red band), the ratio of which is largely modulated by excitation wavelength. Through this feature, the luminescence color of these complexes can be smoothly tuned from deep‐blue to red. Complex [Mn(L5)3][Mn(NCS)4] shows MnII‐based phosphorescence only.

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Section: Resultsmentioning

confidence: 99%

“…Particular interest is devoted to Mn II halide complexes with phosphine oxide ligands , . For instance, some of them, e.g.…”

Section: Introductionmentioning

confidence: 99%

Manganese(II) Thiocyanate Complexes with Bis(phosphine Oxide) Ligands: Synthesis and Excitation Wavelength‐Dependent Multicolor Luminescence

et al. 2020

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“…5). Taking into consideration the information about luminescence spectra given in papers [11,14] and in this study, it is possible to assume the existence of some common mechanisms for FL formation. After analyzing the glow spectra of other Mn-containing compounds [3,4,15], we can assume that the observed glow band corresponds to the glow of the Mn 2+ ion.…”

Section: Results Of Studying the Photoluminescence Spectramentioning

confidence: 99%

“…2 shows microphotographs of the samples obtained at different thicknesses with the help of an optical microscope. Based on the diffraction pattern, it was found that compound N(CH 3 ) 4 Cl и MnCl 2 is crystallized in a monoclinic lattice with spatial group P2 1 /c (14) at 270 K. No impurity phases were detected [3]. The excitation spectra and glow of FL at liquid helium temperature were measured using the Horiba/Jobin-Yvon Fluorolog-3 spectrofluorometer (France), which is equipped with a continuous xenon lamp (450 W) and a photomultiplier Hamamatsu R928P (Japan).…”

Section: The Procedures Of Synthesis and Study Of Photoluminescence Spmentioning

confidence: 99%

Influence of phase transitions on the temperature behavior of photoluminescence spectra in a (N(CH3)4)2MnCl4 crystal

Ільчук

Kashuba

Kuno

et al. 2020

EEJET

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24 1. Introduction Compounds (N(CH 3) 4) 2 MеCl 4 (Me=Mn, Co, Zn) are of interest both in terms of basic science and in practical terms. The simultaneous existence of organic and inorganic components in the crystal structure determines the complex of properties characteristic of both organic and inorganic substances. Inorganic components determine their electrical, magnetic, and thermal properties, while the organic part provides crystals with plastic and luminescent properties.

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“…firstly reported the observation of luminescence for manganese(II) complexes with a square‐pyramidal geometry (C 4v ) of the metal, which is dependent on a suitable temperature. [ 41 ] However, these rarely reported five‐coordinated manganese(II) complexes exhibit the low luminescence efficiency, [ 35,41 ] which severely impedes their practical applications, especially for X‐ray scintillators which require high PLQY to achieve high light outcoupling efficiency for better X‐ray imaging performance. Accordingly, the exploration of Mn 2+ emission in nonclassical surrounding is of great significance and necessity not only for understanding the fundamental relationship between crystal structures and properties but also for developing highly competitive manganese(II) complex scintillators.…”

Section: Introductionmentioning

confidence: 99%

Highly Emissive and Stable Five‐Coordinated Manganese(II) Complex for X‐Ray Imaging

Meng

Zhu

et al. 2021

Laser & Photonics Reviews

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Nowadays, the development of X‐ray imaging has promoted the demand for new‐type scintillators, among which low‐toxic manganese(II) complexes have attracted burgeoning research interest. Herein, a highly stable manganese(II) complex with peculiar five‐coordinated modes is reported, which exhibits strong yellow emission peaked at 583 nm originating from d‐d transition of Mn2+ with high photoluminescence quantum yield (PLQY) up to 93%. The five‐coordinated manganese(II) complex has been rarely reported so far which is an innovative spot in the field of photofunctional metal complex. Thanks to the high PLQY and relatively large stokes shift, the manganese(II) complex yields bright yellow emission under low‐dose X‐ray irradiation and delivers excellent linear response to X‐ray, highlighting its suitability for X‐ray contrast imaging. Based on this, highly resolved X‐ray imaging is successfully achieved that can meet the requirements of many application scenarios. In addition, this manganese(II) complex demonstrates excellent radiation hardness, humidity resistance, and heat stability, indicating the application potential of scintillators in harsh environments. This research not only provides guidance for the design and fabrication of highly luminescent manganese(II)‐based complexes, but also demonstrates the potential of manganese(II)‐based complexes as scintillators for X‐ray imaging technology.

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Luminescence of the Mn²⁺ ion in non-O_h and T_d coordination environments: the missing case of square pyramid

Abstract: The luminescence of Mn2+ ion in a square-pyramidal (C4v) ligand field was discovered. The molecular complexes with such coordination geometry exhibit red emission with enhanced Stokes shift and millisecond lifetimes.

Cited by 48 publications

References 52 publications

Manganese(II) Thiocyanate Complexes with Bis(phosphine Oxide) Ligands: Synthesis and Excitation Wavelength‐Dependent Multicolor Luminescence

Manganese(II) Thiocyanate Complexes with Bis(phosphine Oxide) Ligands: Synthesis and Excitation Wavelength‐Dependent Multicolor Luminescence

Influence of phase transitions on the temperature behavior of photoluminescence spectra in a (N(CH3)4)2MnCl4 crystal

Highly Emissive and Stable Five‐Coordinated Manganese(II) Complex for X‐Ray Imaging

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