Ligand-Centered Near-Infrared Luminescence from Lanthanide Complexes with Chelating Nitronyl Nitroxide Free Radicals

Lescop, Christophe; Luneau, Dominique; Bussière, Guillaume; Triest, Myriam; Reber, Christian

doi:10.1021/ic0004941

Cited by 54 publications

(38 citation statements)

References 17 publications

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“…Most nitronyl nitroxides and their metal complexes show absorption spectra with resolved patterns as illustrated in Figs. 2, 3, and 7, consisting of a sequence of four to six peaks [26,27,30]. The energy differences between these maxima are constant within experimental precision, with the exception of the interval between the two lowest-energy peaks labeled a and b in the absorption spectra.…”

Section: Spectroscopic Characterization Of the Lowest-energy Excited mentioning

confidence: 81%

“…This progression indicates a significant distortion along a low-frequency normal coordinate at all temperatures, likely involving radical-lanthanide-radical modes, as it is not observed for complexes with only one radical ligand or for uncoordinated radicals. The shape of the spectrum does not change with temperature, indicating that the assumption of temperature-indepen- [27] b [33] c [52] d [29] e [26] dent exchange coupling parameters is justified. In contrast, narrower lowtemperature spectra as shown in Fig.…”

Section: Phenomenological Correlations Between Optical Spectra and Mamentioning

confidence: 90%

“…1. The ligator atoms of the radicals are marked by asterisks, based on the crystallographic structures of the complexes [26,27,33].…”

Section: Summary Of Experimental Informationmentioning

confidence: 99%

“…This sensitive instrument was also used to measure luminescence spectra at wavelengths shorter than 1000 nm [35]. Samples were cooled in a liquid helium flow cryostat designed for this microscope (Janis Research Supertran ST-500) [26].…”

Section: Summary Of Experimental Informationmentioning

confidence: 99%

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Excited States and Optical Spectroscopy of Nitronyl Nitroxides and their Lanthanide and Transition Metal Complexes

Bussire¹,

Beaulac²,

Blisle³

et al.

Transition Metal and Rare Earth Compounds

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Section: Spectroscopic Characterization Of the Lowest-energy Excited mentioning

confidence: 81%

Section: Phenomenological Correlations Between Optical Spectra and Mamentioning

confidence: 90%

“…1. The ligator atoms of the radicals are marked by asterisks, based on the crystallographic structures of the complexes [26,27,33].…”

Section: Summary Of Experimental Informationmentioning

confidence: 99%

Section: Summary Of Experimental Informationmentioning

confidence: 99%

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Excited States and Optical Spectroscopy of Nitronyl Nitroxides and their Lanthanide and Transition Metal Complexes

Bussire¹,

Beaulac²,

Blisle³

et al.

Transition Metal and Rare Earth Compounds

Self Cite

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“…Similar behaviors are frequently observed when radicals are used as ligands for Ln III ions. [47] This behavior results from an overlap between the radical excitation band above 500 nm and all (or part of) the emission bands for the Eu III and Tb III ions, thus quenching the Ln luminescence through re-absorption of the metal emission by the radical ligand. In agreement with the latter hypothesis, this quenching is not operative when the aHÀ PTMTC molecule is used as a ligand.…”

Section: Resultsmentioning

confidence: 99%

Three‐Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals

Datcu

Roques

Jubera

et al. 2011

Chemistry A European J

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Lanthanide coordination polymers {[Ln(PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1), Gd (2), and Eu (3)] and {[Ln(αH-PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1'), Gd (2'), and Eu (3')] have been prepared by reacting Ln(III) ions with tricarboxylate-perchlorotriphenylmethyl/methane ligands that have a radical (PTMTC(3-)) or closed-shell (αH-PTMTC(3-)) character, respectively. X-ray diffraction analyses reveal 3D architectures that combine helical 1D channels and a fairly rare (6,3) connectivity described with the (4(2).8)·(4(4).6(2).8(5).10(4)) Schäfli symbol. Such 3D architectures make these polymers porous solids upon departure of the non-coordinated guest-solvent molecules as confirmed by the XRD structure of the guest-free [Tb(PTMTC)(EtOH)(2)H(2)O] and [Tb(αH-PTMTC)(EtOH)(2)H(2)O] materials. Accessible voids represent 40% of the cell volume. Metal-centered luminescence was observed in Tb(III) and Eu(III) coordination polymers 1' and 3', although the Ln(III)-ion luminescence was quenched when radical ligands were involved. The magnetic properties of all these compounds were investigated, and the nature of the {Ln-radical} (in 1 and 2) and the {radical-radical} exchange interactions (in 3) were assessed by comparing the behaviors for the radical-based coordination polymers 1-3 with those of the compounds with the diamagnetic ligand set. Whilst antiferromagnetic {radical-radical} interactions were found in 3, ferromagnetic {Ln-radical} interactions propagated in the 3D architectures of 1 and 2.

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Syntheses, Structures, and Spectroscopic Properties of Cobalt(III) Complexes Containing 3- or 4-Pyridyl-Substituted Nitronyl and Imino Nitroxide Ligands

Ogita¹,

Yamamoto²,

Suzuki³

et al. 2002

Eur. J. Inorg. Chem.

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Several new cobalt(III) complexes incorporating 4,4,5,5-tetramethyl-2-(3-or 4-pyridyl)imidazolin-1-oxyl 3-oxide (NITnpy) (n = 3 or 4) or 4,4,5,5-tetramethyl-2-(3-or 4-pyridyl)-imidazolin-1-oxyl (IMnpy) have been prepared. The X-ray crystallographic analyses and the spectroscopic investigations have revealed that the nitronyl or imino nitroxides with the radical character are bound through the pyridyl-N atom to a Co III center. There are some influences from the radical unpaired electron toward the Co III complex moiety and those from the coordination of the Co III ion toward the

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Ligand-Centered Near-Infrared Luminescence from Lanthanide Complexes with Chelating Nitronyl Nitroxide Free Radicals

Cited by 54 publications

References 17 publications

Excited States and Optical Spectroscopy of Nitronyl Nitroxides and their Lanthanide and Transition Metal Complexes

Excited States and Optical Spectroscopy of Nitronyl Nitroxides and their Lanthanide and Transition Metal Complexes

Three‐Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals

Syntheses, Structures, and Spectroscopic Properties of Cobalt(III) Complexes Containing 3- or 4-Pyridyl-Substituted Nitronyl and Imino Nitroxide Ligands

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