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R
remaining shorter oligomers on a SEC column (Biobeadsꢀ) in
tetrahydrofuran. The solvent was removed in vacuum and the
green material washed with hot acetone and dried in vacuum
to afford 2 (32 mg, 32%) in the form of a dark green solid.
l
max(tetrahydrofuran)/nm: 346, 441 (h), 614 and 680; nmax(KBr
-1
=
pellets)/cm : 2964, 2870, 1695 nst(C O), 1614, 1489, 1394, 1340,
1286 nst(P O), 1259, 1219, 1138, 1097 nst(C–O–C), 1057, 976
nd oop (C C–H trans), 949, 922, 868, 841, 748, 694, 606, 534 and
=
=
449; dH(500 MHz; THF-d8; Me4Si) 0.5–2.3 (m, CH, CH2, CH3,
=
C(CH3)3), 3.6–4.4 (m, ArOCH2), 6.4–6.9 (brs, Ar–CH2 CH2–
Ar¢), 7.0–7.3 (brs, ArH), 8.2–8.5 (m, PcH) and 8.7–9.8 (m,
PcH); m/z (MALDI, dithranol) 5553 (tetramer), 5240, 5076–5064,
4772–4760, 4208–4194 (trimer), 3903–3892, 3728–3713, 3605–
3598, 3439–3428, 3425–3407, 3340–3328, 3216–3208, 3127–3115,
2859–2847 (dimer), 2379–2367, 1987–1981, 1866–1859, 1777–
1768, 1527–1517, 1510–1501 (monomer), 1403–1394, 1386–1379;
SEC (DMF, PS standards): Mw = 7211; Mn = 5132; PD = 1.4;
TGA (◦C/mass lost): 382/-49%, 477/-7%.
Conclusions
Diformylphthalocyanine 3 was a key monomer in the synthesis
of two poly(p-phenylenevinylene) oligomers (oPPV) 1 and 2
laterally substituted by phthalocyanines (Pc). Knoevenagel and
Wadsworth–Horner–Emmons reactions were employed for this
purpose, respectively. The functionalised conjugated oligomers
appears to be a viable way for the preparation of ambipo-
lar conducting “double-cable” polymers (p–n type polymers)
with potential applications in organic solar cells. Photophysical
investigations—by means of fluorescence and transient absorp-
tion measurements—further corroborated the potential of our
approach. In particular, all the features that the ZnPc reveals in
a reference are principally preserved in 1 and 2, despite the high
ZnPc loading.
Acknowledgements
The authors gratefully acknowledge financial support from the
Spanish MEC (CTQ2008–00418/BQU, Consolider-Ingenio 2010
CSD2007–00010 Nanociencia Molecular), Comunidad de Madrid
(MADRISOLAR, S-0505/PPQ/000225) and European Union
(SOLAR n-TYPE, MRTN CT- 2006–035533) is greatly appre-
ciated (T. T.). This work was also supported by the Deutsche
Forschungsgemeinschaft through SFB583, DFG (GU 517/4–1),
FCI, and the Office of Basic Energy Sciences of the U.S. Depart-
ment of Energy (D. M. G.).
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3962 | Dalton Trans., 2009, 3955–3963
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