Green-emitting manganese (II) complexes with phosphoramide and phenylphosphonic diamide ligands

Bortoluzzi, Marco; Castro, Jesús; Enrichi, Francesco; Vomiero, Alberto; Busato, Marta; Huang, Weiguo

doi:10.1016/j.inoche.2018.04.023

Cited by 44 publications

(16 citation statements)

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“…The organophosphorus/arsenic oxygen derivatives are important class of ligands, which can successfully be used to design the monodentate ligand-based neutral phosphorescent manganese(II) complexes. [52,49,[53][54][55][56][57] The monodentate ligandbased neutral manganese(II) complexes usually consist of two monodentate organophosphorus/arsenic oxide ligands and another two halogen atoms (such as Cl, Br, I). Typical chemical www.advopticalmat.de © 2020 Wiley-VCH GmbH structures of these complexes (1a-1c, 2a-2e, and 3a-3c) are given in Scheme 1.…”

Section: Manganese(ii) Complexes Based On Monodentate Ligandsmentioning

confidence: 99%

“…The halogen atoms have remarkable influence on both τ and Φ, and the more heavy iodine-based complexes show much shorter τ of 112-188 µs than that of the bromine-based complexes (479-594 µs). [54][55][56] This phenomenon can be explained by the heavy atom effect of halogen atoms. With the atomic weight increasing from Cl to I, the spin-orbit coupling interactions in these complexes become larger and hence result in a reduction in the lifetime of the excited state.…”

Section: Manganese(ii) Complexes Based On Monodentate Ligandsmentioning

confidence: 99%

“…[57] However, the bromine-based complexes 2b and 2d show moderate quantum efficiencies of 15-19% for phosphorescence, while the iodine-based complexes 2c and 2e exhibit weaker phosphorescence with efficiencies of less than 1% ( Table 1). [54][55][56] The quite low quantum efficiency of the iodine-based complexes may be due to the quenching effect of heavy iodine atom in the complexes.…”

Section: Manganese(ii) Complexes Based On Monodentate Ligandsmentioning

confidence: 99%

“…Jin and Bortoluzzi et al reported a library of phosphoramide‐based manganese(II) complexes 2a – 2e shown in Scheme 1. [ 54–56 ] By using X‐ray single crystal diffraction, their chemical structures are fully confirmed and are unambiguously proved to possess tetrahedrally coordinated manganese(II) ion in these complexes. Except for the chlorine‐based complex 2a with unclear emission property, at room temperature, these complexes show similar phosphorescence with emission peaks from 516 to 521 nm, which can be attributed to the characteristic 4 T 1 − 6 A 1 radiative transition.…”

Section: Molecular Design Strategies Of Phosphorescent Manganese(ii) mentioning

confidence: 99%

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Phosphorescent Manganese(II) Complexes and Their Emerging Applications

Tao

Liu

Wong

2020

Advanced Optical Materials

100

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light-emitting device (OLED) in 1998, [1] phosphorescent transition-metal complexes, especially for noble metal-based ones (e.g., iridium(III), platinum(II), etc.) as triplet emitters toward highly efficient organic electroluminescence, have aroused extensive attention. [15-21] Owing to strong spin-orbit coupling effect, these complexes may use both singlet and triplet excitons to greatly enhance the efficiency of OLED, breaking the upper limit of the conventional fluorescent device efficiency. Due to their unique properties of excited states, they also have extended their applications in other fields, for instance, catalysis, organic solar cells, organic memory devices, biological sensing and imaging, photodynamic therapy, information recording, and security protection, etc. [22-27] Although extensive works have been done to the design and preparation of phosphorescent materials based on noble metals, these noble metals usually have some disadvantages (such as high cost and low abundance in nature), thereby limiting their practical applications. The relatively abundant and cheap PTMCs of low toxicity have drawn considerable interests very recently. [4,23,24,28-31] Many kinds of non-noble metal-based PTMCs such as copper(I), tungsten(VI), and manganese(II) complexes have emerged rapidly. [4,23-25,28-31] Phosphorescent manganese(II) complexes show great potentials in many applications, due to their features including highly efficient phosphorescence, flexible design in molecular structure, ease of synthesis, and rich physical properties (e.g., triboluminescence, stimuli-responsivity, etc.). [24,25a,32-36] Compared with the noble metals, manganese element with an atomic number of 25 has abundant reserves, is environmentally friendly and inexpensive. Moreover, it has richer valence and coordination mode, which has been widely used in the fields of catalysis, ferroelectric, and magnetic materials. [37-39] Among the various valence states of manganese ion, the divalent manganese ion having a 3d 5 electron configuration has a 4 T 1 − 6 A 1 radiative transition closely related to the crystal field strength. The crystal field strength in the metal complex highly depends on the chemical structure of the ligand and the coordination number. These features make the manganese(II) complexes having rich photophysical properties. By regulating the ligand structure, the organic counterion and the coordination number of the manganese(II) complex, the green, yellow, orange, red, or even near-infrared phosphorescence can be achieved. [23-25,36,40] It Phosphorescent manganese(II) complexes are emerging as a new generation of phosphorescent materials showing great potentials in many applications, owing to their unique features including highly efficient phosphorescence, diverse structural/molecular design, and ease of synthesis, structural diversity, rich physical properties (e.g., triboluminescence, stimuli-responsivity, etc.), high abundance, and low cost. The research on phosphorescent manganese(II) complexes is just in its infancy...

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Section: Manganese(ii) Complexes Based On Monodentate Ligandsmentioning

confidence: 99%

Section: Manganese(ii) Complexes Based On Monodentate Ligandsmentioning

confidence: 99%

Section: Manganese(ii) Complexes Based On Monodentate Ligandsmentioning

confidence: 99%

Section: Molecular Design Strategies Of Phosphorescent Manganese(ii) mentioning

confidence: 99%

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Phosphorescent Manganese(II) Complexes and Their Emerging Applications

Tao

Liu

Wong

2020

Advanced Optical Materials

100

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“…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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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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Mn²⁺‐Based Luminescent Metal Halides: Syntheses, Properties, and Applications

Liang

Xiao

Cai

et al. 2023

Advanced Optical Materials

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Lead‐free metal halides are considered a new generation of optoelectronic materials due to their low toxicity, superior optoelectronic properties, ease of synthesis, structural diversity, and low cost. In particular, Mn2+‐based metal halides have earned intensive attention owing to their high emission quantum efficiency, rich physical properties (e.g., triboluminescence and stimuli‐responsivity), low cost, and toxicity. Due to the different coordination environments of Mn ions, Mn2+‐based metal halides can exhibit green, red, and near‐infrared emissions. This review summarizes the recent progress of Mn2+‐based metal halides in synthesis methods, emission mechanisms, photophysical properties, and representative applications in X‐ray scintillations, white light‐emitting diodes, optical anti‐counterfeiting technologies, and fluorescent sensors. Finally, the challenges and potential research directions toward developing Mn2+‐based metal halides are also predicted.

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Green-emitting manganese (II) complexes with phosphoramide and phenylphosphonic diamide ligands

Cited by 44 publications

References 46 publications

Phosphorescent Manganese(II) Complexes and Their Emerging Applications

Phosphorescent Manganese(II) Complexes and Their Emerging Applications

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

Mn²⁺‐Based Luminescent Metal Halides: Syntheses, Properties, and Applications

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Green-emitting manganese (II) complexes with phosphoramide and phenylphosphonic diamide ligands

Cited by 44 publications

References 46 publications

Phosphorescent Manganese(II) Complexes and Their Emerging Applications

Phosphorescent Manganese(II) Complexes and Their Emerging Applications

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

Mn2+‐Based Luminescent Metal Halides: Syntheses, Properties, and Applications

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Mn²⁺‐Based Luminescent Metal Halides: Syntheses, Properties, and Applications