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. 2013 Oct 1;99(1):10.1016/j.dyepig.2013.04.024.
doi: 10.1016/j.dyepig.2013.04.024.

β-Pyrazino-fused tetrarylporphyrins

Federica Mandoj  1 , Sara Nardis  1 , Rajesh Pudi  1 , Larisa Lvova  1 , Frank R Fronczek  2 , Kevin M Smith  2 , Luca Prodi  3 , Damiano Genovese  3 , Roberto Paolesse  4
Affiliations

β-Pyrazino-fused tetrarylporphyrins

Federica Mandoj et al. Dyes Pigm. .

Abstract

A novel method for the preparation of β-fused porphyrin dyads was developed that exploits a one-pot reaction of 2,3-diaminoporphyrins with diethyl oxalate. This approach provides good yields of the zinc β-fused dyad and the corresponding free-base, opening the way for preparation of several metal derivatives to permit modulation of optoelectronic characteristics for commercial applications.

Keywords: 2,3-Diaminoporphyrin; DSSC; Dietyl oxalate; Porphyrin dyad electrochemistry; α-dione porphyrin; β-fused-porphyrin.

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Figures

Fig. 1
Fig. 1
Molecular structure of 4a with 50% ellipsoids: a) front view; b) side view.
Fig. 2
Fig. 2
Absorption spectra of dyads in CH2Cl2.
Fig. 3
Fig. 3
Absorption (solid line) and fluorescence (dotted line) spectra of 4a in CH2Cl2.
Fig. 4
Fig. 4
Cyclic voltammograms of 4a and ZnTPP.
Fig. 5
Fig. 5
Cyclic voltammogram of dyad 4a; first scan toward oxidation.
Scheme 1
Scheme 1
Synthesis of 4a by condensation of 2,3-diaminoporphyrin zinc complex 2 with zinc α-dione porphyrin derivative 3.
Scheme 2
Scheme 2
Synthesis of 4a by condensation of 2,3-diaminoporphyrin zinc complex 2 with diethyl oxalate. i) CHCl3/TFA, r.t. ii) Cu(OAc)2 • H2O, CHCl3/MeOH, Δ, 2 h.
Scheme 3
Scheme 3
Proposed reaction mechanism for the formation of 4a and 3. i) 2/diethyl oxalate ratio of 1:25, CH2Cl2/MeOH, Δ, 6 h; ii) 2/diethyl oxalate ratio of 1:40, CH2Cl2/MeOH, Δ, 6 h.
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