Subphthalocyanine dimer

One example of a dimeric subphthalocyanine has recently been reported. This macrocycle (2.332) was prepared by condensing of an excess of 4-r-butylphtha-lonitrile 2.278 with 1,2,4,5-tetracyanobenzene (2.331) in the presence of Ph2BBr. The resulting laterally bridged system 2.332 is obtained in 2.8% yield (along with a 24% yield of the monomeric subphthalocyanine 2.286) (Scheme 3.14). Despite the presumed non-planar nature of the subphthalocyanine units, H NMR data collected for this system indicate that it, like the monomeric systems discussed above, is aromatic. On the other hand, compound 2.332 displays spectral properties that differ dramatically from those of the monomeric macrocycle 2.286. For instance, compared to that of 2.286, the UV-vis absorption spectrum of 2.332 is rather featureless, although absorption bands are observed in nearly the same spectral region as in the case of 2.286. The emission spectrum of 2.332 also resembles that of the mono-... 

Another Interesting ir-extended subphthalocyanine derivative that would be worthwhile to compare with standard SubPc is the fused subphthalocyanine dimer 16 whose NLO properties have not been yet studied (Figure 11) [69], The presence of two isomers possessing very different dipole moment but identical TT-surfaces should give rise to interesting differences that may contribute to the understanding of the NLO behavior of this type of TT-extended molecules. 

In the case of tetracarbonitriles very interesting fused dimeric and trimeric subphthalocyanines can be obtained [100,103] (Scheme 46). Thus, co-condensation of TFPN, pyromeUitic tetranitrile (1,2,4,5-tetracyanobenzene) 182 and BCI3 (10 1 36 ratio) in p-xylene under reflux (3 h) gives along with the monomeric [ClBSubPcFij] 176 (43 %), dimeric 183 (20 %) and trimeric 184 (3 %) forms [103, 104]. It was shown [104] that 10 1 ratio of dinitriles TPPN 182 affords the highest yield of dimers 183 (16 % at 20 1 and 5 % at 5 1 ratio) in these reaction conditions. 

Scheme 46 Synthesis of dimeric and trimeric fluorinated subphthalocyanines...

Claessens CG, Torres T (2002) Synthesis, separation, and characterization of the topoisomers of fused bicyclic subphthalocyanine dimers. Angew Chem 114 2673-2677 [Angew Chem Int Ed 41 2561-2565]... 

Iglesias RS, Claessens CG, Torres T, Herranz MA, Ferro VR, Garcia de la Vega JM (2007) Subphthalocyanine-fused dimers and trimers synthetic, electrochemical, and theoretical studies. J Org Chem 72 2967-2977... 

Iglesias RS, Qaessens CG, Torres T, Aminur Rahman GM, Guldi DM (2005) Synthesis and photophysical characterization of a subphthalocyanine fused dimer-Ca) dyad. Chem Commun 2005 2113-2115... 

Iglesias RS, Qaessens CG, Aminur Rahman GM, Herranz MA, Guldi DM, Torres T (2(X)7) Subphthalocyanine fused dimers-C6o dyads synthesis, characterization, and theoretical study. Tetrahedron 63 12396-12404... 

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