TY - JOUR
T1 - Peripherally metalated secoporphyrazines
T2 - A new generation of photoactive pigments
AU - Sakellariou, Efstathia G.
AU - Montalban, Antonio Garrido
AU - Meunier, Hubert G.
AU - Rumbles, Garry
AU - Phillips, David
AU - Ostler, Richard B.
AU - Suhling, Klaus
AU - Barrett, Anthony G M
AU - Hoffman, Brian M.
PY - 2002/4/22
Y1 - 2002/4/22
N2 - Base-catalyzed cross condensation of dipropylmaleonitrile 1 with bis(dimethylamino)maleonitrile 2 in an equimolar ratio afforded the porphyrazines 3a, 4a, 5a, 6a and 7a. Subsequent demetalation of 5a with TFA followed by remetalation with Zn(OAc)2 gave ligand 5c in good yield. Compound 5c was, in turn, selectively oxidized and further peripherally functionalized using Pt(PhCN)2Cl2 and PdCl2 to yield the novel seco solitaire porphyrazines 1Oa and 10b. The photophysical profiles of the seco solitaire porphyrazines 10a and 10b were evaluated by means of absorption, emission, and transient absorption spectroscopy. The new pigments 10a and 10b were found to be photochemically more stable than the solitaire complexes 3d and 3e and mediated the generation of singlet oxygen with quantum yields of 0.59 and 0.45, respectively.
AB - Base-catalyzed cross condensation of dipropylmaleonitrile 1 with bis(dimethylamino)maleonitrile 2 in an equimolar ratio afforded the porphyrazines 3a, 4a, 5a, 6a and 7a. Subsequent demetalation of 5a with TFA followed by remetalation with Zn(OAc)2 gave ligand 5c in good yield. Compound 5c was, in turn, selectively oxidized and further peripherally functionalized using Pt(PhCN)2Cl2 and PdCl2 to yield the novel seco solitaire porphyrazines 1Oa and 10b. The photophysical profiles of the seco solitaire porphyrazines 10a and 10b were evaluated by means of absorption, emission, and transient absorption spectroscopy. The new pigments 10a and 10b were found to be photochemically more stable than the solitaire complexes 3d and 3e and mediated the generation of singlet oxygen with quantum yields of 0.59 and 0.45, respectively.
UR - http://www.scopus.com/inward/record.url?scp=0037156139&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0037156139&partnerID=8YFLogxK
U2 - 10.1021/ic0111583
DO - 10.1021/ic0111583
M3 - Article
C2 - 11952372
AN - SCOPUS:0037156139
SN - 0020-1669
VL - 41
SP - 2182
EP - 2187
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 8
ER -