1997
DOI: 10.1021/ic960604x
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EPR Spectra, Luminescence Data, and Radiationless Decay Processes of Copper(II) Porphyrins

Abstract: For a series of copper(II) porphyrins, we report EPR data from solid solutions as well as E 0 values for the first ring oxidation, emission spectra, and luminescence lifetimes in methylene chloride. Although the EPR parameters are fairly constant, the potentials vary by almost 700 mV, and the room-temperature lifetimes range from 300 ns for Cu(TCl2PP) to 15 ns for Cu(TMeOPP), where TCl2PP denotes 5,10,15,20-tetra(2‘,6‘-dichlorophenyl)porphyrin and TMeOPP denotes 5,10,15,20−tetra(4‘-methoxyphenyl)porphyrin. The… Show more

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Cited by 79 publications
(78 citation statements)
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“…[26] This value was corroborated for a series of meso-substituted copper(II) porphyrins (R = aromatic, alkyl, or H) that exhibited phosphorescence lifetimes ranging from 15 to 300 ns (in CH 2 Cl 2 at room temperature). [27] The position of the triplet state was also confirmed from the measurements of the absorption spectra focusing in the 700 nm region to observe the 2 S 0 ! 2 T 1 transitions and the positions of these absorption features (295 K) and of the phosphorescence 0-0 peaks…”
Section: Spectroscopy and Photophysicsmentioning
confidence: 76%
“…[26] This value was corroborated for a series of meso-substituted copper(II) porphyrins (R = aromatic, alkyl, or H) that exhibited phosphorescence lifetimes ranging from 15 to 300 ns (in CH 2 Cl 2 at room temperature). [27] The position of the triplet state was also confirmed from the measurements of the absorption spectra focusing in the 700 nm region to observe the 2 S 0 ! 2 T 1 transitions and the positions of these absorption features (295 K) and of the phosphorescence 0-0 peaks…”
Section: Spectroscopy and Photophysicsmentioning
confidence: 76%
“…Thus, keeping in mind exchange d-p effects known for monomeric Cu-porphyrins [52][53][54][55][56][57][58] and discussed in Introduction, one may conclude that in heterodimers with the intercenter distance R≈10÷12.6 Å the interaction of the unpaired S 0 in the case of Cu-containing components); q, k TT , triplet-triplet energy transfer from thermally equilibrated "trip-doublet" ( 2 T 1 ) and "trip-quartet" ( d-electron of central Cu ion of Cu-porphyrin subunit with p-conjugated system of the other half leads to an increase of the intersystem crossing rate constant in the last one. As a result, the lifetimes of S 1 and T 1 states in the H 2 -and Znsubunits of the heterodimers are reduced compared to those for the corresponding homodimers.…”
Section: ≥2×10mentioning
confidence: 99%
“…In contrast, exchange d-p effects are hardly dependent on temperature. [52][53][54][55][56][57][58][59]62,63,[108][109][110][111][112] ] Experimental findings presented in Figure 5D show that upon temperature lowering from 293 K down to T≈210 K an additional quenching of the non-complexed dimer is still observed caused by the full complexation at low T. At the same time, fluorescence of the complexed dimer (ZnOEP) 2 Ph in the pentad 2(ZnOEP) 2 Ph⊗CuP-(mPyr) 4 remains still strongly quenched like that found at 293 K. The most interesting observation is that upon further temperature lowering (down to 190 K (curve 3), 165 K and 150 K (curve 4), a small pronounced increase of the redshifted fluorescence band belonging to the dimeric subunit in the pentad (like di-pyridinated homodimer (ZnOEP) 2 Ph [74,80] ) is evidently seen. It means that in a temperature range of 150÷293 K the emission strong quenching for both dimers (ZnOEP) 2 Ph in the pentads containing CuP(mPyr) 4 extraligand, is caused by exchanged d-p effects presumably which remain still pronounced even at intercenter distances R DA =8.8 Å.…”
Section: Multiporphyrin Self-assembled Complexes With Cu-porphyrin Sumentioning
confidence: 99%
See 1 more Smart Citation
“…[27,28,30] Metalloporphyrins show wide applicability [31] and in the past two decades the biomimetic catalysis of metalloporphyrins has increasingly attracted significant attention. [32] Among them, porphyrinatocopper complexes, an important class of transition metal complexes, exhibit many interesting properties such as their involvement in electron-transfer reactions, [33,34] luminescence, [35][36][37] sensing, [36] non-linear optical behaviours, [38] biological [39a] and catalytic roles, [39b] magnetic properties, [40] etc. In this paper, we report an efficient, regioselective, one-pot and two-step synthesis of b-hydroxytriazoles from sodium azide, epoxides, and non-activated terminal alkynes by a three-component [41] click reaction, proceeding via the formation of 2-azido alcohols from sodium azide and epoxides.…”
Section: Introductionmentioning
confidence: 99%