Spectroscopic observation of coupled metal-ligand vibrational modes in the luminescence spectrum of trans-[ReO2(1-methylimidazole)4]I

Savoie, Carole; Reber, Christian; Bélanger, Suzanne; Beauchamp, André L.

doi:10.1021/ic00119a001

Cited by 24 publications

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“…1-3 Rhenium complexes with amines and derivatives of pyridine and imidazole are used for studying electron transfer, oxygen atom transfer, electrocatalysis, luminescence, and fluorescence. [4][5][6][7][8] Complexes with nitroimidazoles and nitropyrazoles have found application as markers for hypoxic tumor cells. 9, 10 These aspects of the chemistry of rhenium complexes with pyridine and imidazole derivatives have been studied in depth.…”

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Rhenium(IV) and rhenium(V) complexes with 3,5-dimethylpyrazole

et al. 2006

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Mono and dinuclear Re IV and Re V complexes with 3,5 dimethylpyrazole (Me 2 pzH) were synthesized. The cis [Re 2 O 3 Cl 4 (3,5 Me 2 pzH) 4 ] complex (cis 1) was prepared by the reaction of NH 4 ReO 4 with K[HB(Me 2 pz) 3 ] in concentrated HCl or by refluxing of [ReCl 3 (MeCN)(PPh 3 ) 2 ] with Me 2 pzH in air. The bromide complex trans [Re 2 O 3 Br 4 (3,5 Me 2 pzH) 4 ] (trans 2) was synthesized by passing dry HBr through a solution of [Re 2 O 3 Br 2 (µ 3,5 Me 2 pz) 2 (3,5 Me 2 pzH) 2 ] (4) in chloroform. The pyrazolate bridged complex [Re 2 O 3 Cl 2 (µ 3,5 Me 2 pz) 2 (3,5 Me 2 pzH) 2 ] (3) was prepared from (Et 4 N) 2 [ReOCl 5 ] or Cs 2 [ReOCl 5 ] and Me 2 pzH. The corresponding bromide and iodide complexes [Re 2 O 3 X 2 (3,5 Me 2 pz) 2 (3,5 Me 2 pzH) 2 ]•C 6 H 6 (X = Br (4) or I (5)) were synthesized by the reactions of (NH 4 ) 2 [ReBr 6 ] or K 2 [ReI 6 ], respectively, with Me 2 pzH. The [ReO(OMe)(3,5 Me 2 pzH) 4 ]Br 2 • •3,5 Me 2 pzH•4H 2 O complex (6) was obtained as a by product in the synthesis of complex 4. The reaction of [ReNCl 2 (PPh 3 ) 2 ] with Me 2 pzH was accompanied by hydrolytic denitration giving rise to the mixed ligand complex [Re 2 O 3 Cl 2 (µ 3,5 Me 2 pz) 2 (3,5 Me 2 pzH)(PPh 3 )] (7). The reaction of (NH 4 ) 2 [ReBr 6 ] with a Me 2 pzH melt gave the trans [ReBr 4 (3,5 Me 2 pzH) 2 ]• •Me 2 CO complex (8). The structures of complexes 2 and 4-8 were established by X ray diffraction. All compounds were characterized by elemental analysis, electronic absorption spectroscopy, 1 H NMR and IR spectroscopy, mass spectrometry, and cyclic voltammetry.

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Rhenium(IV) and rhenium(V) complexes with 3,5-dimethylpyrazole

et al. 2006

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“…Complexes of Re V with metal-ligand multiple bonds have received considerable attention due to their reactivity, photochemical and spectroscopic properties. [1][2][3][4] We have studied a series of trans-dioxo complexes of Re V and Os VI with imidazole, carboxylate and ethylenediamine ligands 5,6 and have discovered near-IR (NIR) luminescence bands that are lower in energy by several thousand wavenumbers than the luminescence maximum of the well known trans-[ReO 2 (py) 4 ] + , a representative trans-dioxorhenium(v) compound. 7,8 Oxorhenium(v) complexes with low-energy emissions could lead to a novel spin-crossover transition expected for tetragonal 5d 2 complexes.…”

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Large variation of the luminescence energy from rhenium(V) complexes with oxo and nitrido ligands

Oetliker¹,

Savoie²,

Reber³

et al. 1998

Chem. Commun.

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“…The intensity distribution within this cluster of bands is not identical along the progression. This is an experimental evidence for coupled coordinates, 5,6,14,15 discussed and illustrated in the following discussion.…”

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confidence: 71%

Vibronic structure in the luminescence spectra of tetragonal d2 and d8 complexes analyzed by wavepacket dynamics on two-dimensional potential surfaces

Triest¹,

Masson²,

Grey³

et al. 2000

PhysChemComm

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The luminescence spectra of the tetragonal trans-ReO 2 (vinylimidazole) 4+ complex and the square planar Pd(SCN) 4 2and Pt(SCN) 42complexes all show vibronic progressions in two predominant vibrational modes. In the first complex, the vibronic progressions involve high-frequency and low-frequency metal-ligand modes. In the square planar complexes, the two vibrational modes have similar frequencies. At the intermediate resolution, often observed experimentally, these compounds provide an example of the missing mode (or MIME) effect. Wavepacket dynamics on two-dimensional surfaces explain in a visual and intuitively appealing way the spectroscopic features. The distinct effects are caused by the different frequency ratios between the two modes of the two-dimensional models describing each complex. The emitting state structure determined from the spectra reveals similar changes along a bending normal coordinate for Pd(SCN) 4 2and Pt(SCN) 4 2-.

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Spectroscopic observation of coupled metal-ligand vibrational modes in the luminescence spectrum of trans-[ReO2(1-methylimidazole)4]I

Cited by 24 publications

References 0 publications

Rhenium(IV) and rhenium(V) complexes with 3,5-dimethylpyrazole

Rhenium(IV) and rhenium(V) complexes with 3,5-dimethylpyrazole

Large variation of the luminescence energy from rhenium(V) complexes with oxo and nitrido ligands

Vibronic structure in the luminescence spectra of tetragonal d2 and d8 complexes analyzed by wavepacket dynamics on two-dimensional potential surfaces

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