Dual-emitting Mn(II) and Zn(II) halide complexes with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as ligand

Castro, Jesús; Agostinis, Lodovico; Bortoluzzi, Marco

doi:10.1016/j.ica.2022.121285

Cited by 12 publications

(7 citation statements)

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“…For instance, non-linear optical properties were observed for [ZnCl 2 (O=PPh 3 ) 2 ] [ 32 ], and Zn(II) halide complexes with N , N , N ′, N ′-tetramethyl- P -indol-1-ylphosphonic diamide showed intense green phosphorescence [ 33 ]. Given our interest in the preparation of luminescent metal complexes with phosphonates and cyclic organophosphorus compounds [ 34 , 35 , 36 , 37 ], we synthesized the two enantiomers of O=PPh(BINOL), and we started investigating the luminescent properties of the related Zn(II) and Mn(II) halide complexes. The preliminary results, together with the single-crystal X-ray structure determination of ( S )-O=PPh(BINOL), are provided in this communication.…”

Section: Introductionmentioning

confidence: 99%

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Ferraro,

Castro,

Bortoluzzi

2024

Molecules

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The two enantiomers of chiral phosphonate 4-phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide, O=PPh(BINOL), were synthesized from the proper 1,1′-bi-2-naphtol (BINOL) enantiomer and characterized. The structure of the (S)-enantiomer was elucidated by means of single-crystal X-ray diffraction. The reaction with anhydrous ZnBr2 afforded complexes having the general formula [ZnBr2{O=PPh(BINOL)}2] that showed intense fluorescence centered in the near-UV region rationalized on the basis of TD-DFT calculations. The corresponding Mn(II) complexes with the general formula [MnX2{O=PPh(BINOL)}2] (X = Cl, Br) exhibited dual emission upon excitation with UV light, with the relative intensity of the bands dependent upon the choice of the halide. The highest energy transition is comparable with that of the Zn(II) complex, while the lowest energy emission falls in the red region of the spectrum and is characterized by lifetimes in the hundreds of microseconds range. Although the emission at lower energy can also be achieved by direct excitation of the metal center, the luminescence decay curves suggest that the band in the red range is possibly derived from BINOL-centered excited states populated by intersystem crossing.

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Section: Introductionmentioning

confidence: 99%

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Ferraro,

Castro,

Bortoluzzi

2024

Molecules

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“…In the octahedral environment, the red emission is associated with a higher Mn-Mn coupling interaction resulting from short Mn-Mn distances (3–5 Å) [ 27 , 28 ]. Apart from the single green or red emission bands, dual emission has also been reported in a few cases due to the coexistence of both environments and/or from electron-phonon coupling variation [ 29 , 30 , 31 ]. Triboluminescence is another interesting phenomenon that has been observed in non-centrosymmetric crystals of Mn (II) complexes owing to its great potential in structural damage sensing, stress sensing, display, and security marking [ 32 , 33 , 34 , 35 ].…”

Section: Introductionmentioning

confidence: 99%

“…Another issue to consider for a better understanding of Mn-based perovskite spectroscopy is to explore the role played by the organic ligand on the structure and photobehavior. Few reports have suggested the involvement of electron-phonon interactions in their photochemistry [ 29 , 30 , 31 ]. To gain insight into the electronic structure, the origin of bright photoluminescence, and ferromagnetic coupling in these kinds of materials, several ab initio models have been proposed [ 41 , 42 ].…”

Section: Introductionmentioning

confidence: 99%

The Effects of Mono- and Bivalent Linear Alkyl Interlayer Spacers on the Photobehavior of Mn(II)-Based Perovskites

Rakshit

Medina

Lezama

et al. 2023

IJMS

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Mn(II)-based perovskite materials are being intensively explored for lighting applications; understanding the role of ligands regarding their photobehavior is fundamental for their development. Herein, we report on two Mn (II) bromide perovskites using monovalent (perovskite 1, P1) and bivalent (perovskite 2, P2) alkyl interlayer spacers. The perovskites were characterized with powder X-ray diffraction (PXRD), electron spin paramagnetic resonance (EPR), steady-state, and time-resolved emission spectroscopy. The EPR experiments suggest octahedral coordination in P1 and tetrahedral coordination for P2, while the PXRD results demonstrate the presence of a hydrated phase in P2 when exposed to ambient conditions. P1 exhibits an orange-red emission, while P2 shows a green photoluminescence, as a result of the different types of coordination of Mn(II) ions. Furthermore, the P2 photoluminescence quantum yield (26%) is significantly higher than that of P1 (3.6 %), which we explain in terms of different electron-phonon couplings and Mn-Mn interactions. The encapsulation of both perovskites into a PMMA film largely increases their stability against moisture, being more than 1000 h for P2. Upon increasing the temperature, the emission intensity of both perovskites decreases without a significant shift in the emission spectrum, which is explained in terms of an increase in the electron-phonon interactions. The photoluminescence decays fit two components in the microsecond regime—the shortest lifetime for hydrated phases and the longest one for non-hydrated phases. Our findings provide insights into the effects of linear mono- and bivalent organic interlayer spacer cations on the photophysics of these kinds of Mn (II)-based perovskites. The results will help in better designs of Mn(II)-perovskites, to increase their lighting performance.

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“…Zinc( ii ) and cadmium( ii ) complexes establish one of the most important classes of emissive compounds. 71–121 Earlier, we synthesized a series of mononuclear zinc( ii ) and cadmium( ii ) complexes with hybrid ligands containing a 2,2′-bipyridine moiety and natural terpene (+)-limonene or (+)-3-carene moieties and demonstrated that they exhibit luminescence with the quantum yield increasing in the following order: free ligand < cadmium( ii ) complex < zinc( ii ) complex. 122 The complexes with the limonene derivative demonstrate excitation wavelength–dependent emission with nanosecond and microsecond lifetimes of the excited states.…”

Section: Introductionmentioning

confidence: 99%

Efficient emission of Zn(ii) and Cd(ii) complexes with nopinane-annelated 4,5-diazafluorene and 4,5-diazafluoren-9-one ligands: how slight structural modification alters fluorescence mechanism

et al. 2023

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Dual-emitting Mn(II) and Zn(II) halide complexes with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as ligand

Cited by 12 publications

References 70 publications

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

The Effects of Mono- and Bivalent Linear Alkyl Interlayer Spacers on the Photobehavior of Mn(II)-Based Perovskites

Efficient emission of Zn(ii) and Cd(ii) complexes with nopinane-annelated 4,5-diazafluorene and 4,5-diazafluoren-9-one ligands: how slight structural modification alters fluorescence mechanism

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