Chemiluminescence of organometallics in solution

Булгаков, Р. Г.; Казаков, В. П.; Толстиков, Г. А.

doi:10.1016/0022-328x(90)87299-s

Cited by 24 publications

(13 citation statements)

References 47 publications

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“…The results of these experiments and known data 1,2 sug gest that the ESR signal belongs to the EtС 60 • FR formed upon photodissociation of the dimer in the reaction . (9) An additional support for this conclusion could be the coincidence of the g factor measured by us with the lit erature value. However, known data on FR of the RC 60 • type are restricted by the data on MeC 60 • only (g = 2.00229 and 2.00231 for different sources of radicals R • ).…”

Section: Resultsmentioning

confidence: 71%

“…27, 44 The BCL emitter ( 3 СН 3 СНО*) appears upon the disproportionation of the RO 2 • radicals in reaction (18). 8, 9 A small portion of the alkyl radicals, which avoid the attack of О 2 by reac tion (15), add to С 60 to form the FR in reaction (20), and they are further transformed into the stable products P (FEH, EF, dimers, and, possibly, trimers) in reaction (21). The energy of the primary emitter 3 СН 3 СНО* is trans ferred to the products of FR transformations.…”

Section: Resultsmentioning

confidence: 99%

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Generation of fullerenyl radicals and chemiluminescence in the (C60—R3Al)—O2 system

et al. 2007

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Fullerenyl radicals (FR) RС 60• and chemiluminescence (CL) are generated in the pres ence of O 2 in С 60 -R 3 Al (R = Et, Bu i ) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R • radical, which is an intermediate of R 3 Al autooxidation, to C 60 . Mass spectroscopy and HPLC were used to identify Et n С 60 H m (n, m = 1-6), Et p C 60 (p = 2-6), and dimer EtС 60 С 60 Et as stable products of FR transformations. As found by ESR, the EtС 60 • radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C 60 -R 3 Al)-O 2 system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O 2 , which appear as broadening of the ESR signals. Chemiluminescence arising in the (C 60 -R 3 Al)-O 2 system is much brighter (I max = 1.86•10 8 photon s -1 mL -1 ) than the known background CL (I max = 6.0•10 6 photon s -1 mL -1 ) for the autooxidation of R 3 Al and is localized in a longer wavelength spectral region (λ max = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter 3 СН 3 СНО* to the products of FR transformation: R n С 60 H m , R p C 60 , and EtС 60 С 60 Et.

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Section: Resultsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Generation of fullerenyl radicals and chemiluminescence in the (C60—R3Al)—O2 system

et al. 2007

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“…4,13 The intensity of the BGCL was many times smaller than the CL with lanthanide complexes. However, the shapes of kinetic curves in both cases for BGCL and CL were the same (Fig.…”

Section: Resultsmentioning

confidence: 96%

“…4,13,25 The exited 3 Rշ C(H)=O* molecules transfer energy to Eu 2+ converting it into the eleсtronically exited state Eu 2+ * (5), which is deactivated by emitting the green CL (6). When the europium complex is absent in the reaction system (not loaded into the reactor), we observed only very weak BGCL caused by emission of the triplet-excited aldehyde 4,25,13 in a much shorter wavelength 430 nm (6). In Scheme 1, P 2 denotes molecular oxidation products, among which (Bu i O) 2 Al(OH) is the main one.…”

Section: 25mentioning

confidence: 99%

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The first registration of a green liquid-phase chemiluminescence of the divalent Eu²⁺* ion in interaction of β-diketonate complexes Eu(acac)₃·H₂O, Eu(dpm)₃, Eu(fod)₃ and Eu(CH₃COO)₃·6H₂O with Buⁱ₂AlH in THF with the participation of oxygen

2015

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The first liquid-phase green chemiluminescence (CL) of the divalent europium Eu 2+ * at the study of interactions in the systems EuL3•(Н2О)x-THF-Bu i 2AlH-O2 (L = acac, dpm, fod, and CH3COO; x = 0, 1, 6; Bu i = iso-C4H9) was discovered. The attack of Bu i 2AlH on the water of crystallization of complexes EuL3•(Н2О)x affords aluminoxane (Bu i 2Al)2O, hydrogen, and isobutane. The reaction of Bu i 2AlH and EuL3-moiety of the initial Eu 3+ complexes leads to the previously no synthesized divalent europium complexes EuL2•(THF)2, which were isolated and characterized by elemental and spectral analysis in the present work. In the reaction solutions, these complexes are associated in a bulky complexes with an excess of diisobutylaluminum hydride EuL2•(THF)2-Bu i 2AlH. The measured spectra of CL and photoluminescence (PL) of yellow-green reaction solutions in both cases consist of one broad band with λmax = 555±10 nm due to the emission of the electronexcited state of the Eu 2+ * ion (4f 6 5d 1 →4f 7 transition), a part of the bulky complex EuL2•(THF)2-Bu i 2AlH. The lifetime of the excited states, PL, and CL quantum yields of the Eu 2+* ion in the EuL2•(THF)2-Bu i 2AlH complexes were determined. A mechanism ("indirect CL") is proposed to explain the generation of the green CL. The primary emitter triplet-excited isobutyric aldehyde 3 Rշ C(H)=O* (Rշ = iso-C3H7) is formed in the disproportionation reaction of peroxyl radicalsintermediates of Bu i 2AlH oxidation by oxygen. The exited 3 Rշ C(H)=O* molecules transfer energy to Eu 2+ ion converting it into the eleсtronically exited state Eu 2+ *, which is then deactivated by emitting quanta of green light due to the 4f 6 5d 1 →4f 7 transition. It was found that for a divalent Eu 2+ unlike to trivalent Ln 3+ ions, replacement of the inorganic anion-ligand Cl -(complex EuCl2•(THF)2-Bu i 2AlH) with organic one L (complex EuL2•(THF)2-Bu i 2AlH) decreases the CL and PL intensity and leads to the green-shift of the luminescence maximum of Eu 2+* from the blue (λmax = 465 nm) to the green (λmax = 555 nm) region. The high brightness and duration of the CL, visible to the naked eye in the system Eu(fod)3-THF-Bu i 2AlH-O2, make it promising as a chemical source of green light.

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Divalent Eu²⁺ ion – an effective inorganic mediator of energy transfer from the primary chemiluminescence emitter ³Me₂CHC(H)=O* on Tb³⁺ and Ru(bpy)₃²⁺ ions

2018

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This study demonstrated for the first time that chemiluminescence (CL) from oxidation of Bui2AlH (Bu = C4H9) using oxygen from tetrahydrofuran (THF) was significantly enhanced by the addition of Ru(bpy)32+. A quantitative comparison of the enhancement efficiency of this CL was performed by addition of ionic phosphors Eu2+, Tb3+ and Ru(bpy)32+. CL enhancement was caused by energy transfer from the primary CL emitter (3Me2CHC(H)=O* aldehyde) to these ionic phosphors. The CL efficiency enhancement was in the order: Eu2+ (8.9 × 106) > Tb3+ (100) > Ru(bpy)32+ (50). The enhanced CL emitters were excited ions: Eu2+*, λmax = 465 nm; Tb3+*, λmax = 485, 542, 625 nm; and Ru(bpy)32+*, λmax = 567 nm. When two ions Eu2+–Tb3+ or Eu2+–Ru(bpy)32+ were present in the reaction solution, the efficiency of CL enhancement by Tb3+ or Ru(bpy)32+ ions was much higher, being 1.2 × 106 and 4.2 × 104, respectively. In this case, two excited ions were simultaneously registered as CL emitters: Eu2+* and Tb3+* or Eu2+* and Ru(bpy)32+*. Emission intensity of the Eu2+* ion in these emitter doublets is much lower than when only one Eu2+ ion is present in solution.

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Chemiluminescence of organometallics in solution

Cited by 24 publications

References 47 publications

Generation of fullerenyl radicals and chemiluminescence in the (C60—R3Al)—O2 system

Generation of fullerenyl radicals and chemiluminescence in the (C60—R3Al)—O2 system

The first registration of a green liquid-phase chemiluminescence of the divalent Eu²⁺* ion in interaction of β-diketonate complexes Eu(acac)₃·H₂O, Eu(dpm)₃, Eu(fod)₃ and Eu(CH₃COO)₃·6H₂O with Buⁱ₂AlH in THF with the participation of oxygen

Divalent Eu²⁺ ion – an effective inorganic mediator of energy transfer from the primary chemiluminescence emitter ³Me₂CHC(H)=O* on Tb³⁺ and Ru(bpy)₃²⁺ ions

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Chemiluminescence of organometallics in solution

Cited by 24 publications

References 47 publications

Generation of fullerenyl radicals and chemiluminescence in the (C60—R3Al)—O2 system

Generation of fullerenyl radicals and chemiluminescence in the (C60—R3Al)—O2 system

The first registration of a green liquid-phase chemiluminescence of the divalent Eu2+* ion in interaction of β-diketonate complexes Eu(acac)3·H2O, Eu(dpm)3, Eu(fod)3 and Eu(CH3COO)3·6H2O with Bui2AlH in THF with the participation of oxygen

Divalent Eu2+ ion – an effective inorganic mediator of energy transfer from the primary chemiluminescence emitter 3Me2CHC(H)=O* on Tb3+ and Ru(bpy)32+ ions

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The first registration of a green liquid-phase chemiluminescence of the divalent Eu²⁺* ion in interaction of β-diketonate complexes Eu(acac)₃·H₂O, Eu(dpm)₃, Eu(fod)₃ and Eu(CH₃COO)₃·6H₂O with Buⁱ₂AlH in THF with the participation of oxygen

Divalent Eu²⁺ ion – an effective inorganic mediator of energy transfer from the primary chemiluminescence emitter ³Me₂CHC(H)=O* on Tb³⁺ and Ru(bpy)₃²⁺ ions