Discotic liquid crystals of transition metal complexes 50(dagger): spiranthes-like supramolecular structure of phthalocyanine-fullerene dyads

We have synthesized novel liquid crystalline Pc-C-60 dyads (CnS)(6)PcCu-C-60 (n = 14, 16, 18: 1a-1c) by using our developed synthetic method in order to investigate the mesomorphism and alignment behavior. Each of the (CnS)(6)PcCu-C-60 dyads shows perfect homeotropic alignment in the Col(ho) mesophase between two glass plates for n = 14, 16, 18 and also on a glass plate for n = 14, although none of the parent Pc compounds (CnS)(8)PcCu and the Pc precursors (CnS)(6)PcCu-OH and (CnS)(6)PcCu-OFBA shows homeotropic alignment. It may be attributed to the strong affinity between fullerene and glass surface. Although the reason is not so clear at the present time, this is very useful guideline for the molecular design to prepare homeotropic alignment-showing discotic liquid crystals. Very interestingly, the spherical C-60 parts form a helical structure around the column formed by the disk-like Pc parts. This supramolecular structure very resembles spiranthes. The spiranthes-like supramolecular structure is compatible with one-dimensional nano-array expecting the high conversion efficiency of solar cells.ArticleJOURNAL OF PORPHYRINS AND PHTHALOCYANINES. 18(5):366-379 (2014)journal articl

Discotic liquid crystals of transition metal complexes 48: Synthesis of novel phthalocyanine-fullerene dyads and effect of a methoxy group on their clearing points

In our previous work, we could successfully synthesize the 1:1 phthalocyanine-fullerene (Pc-C-60) dyads, (OFbaC(60))PcCu(OCH3) 2, in very high yields (81 similar to 96%) by using Prato reaction. In this study, we have prepared novel Pc-C-60 dyads, (OFbaC(60)) PcM (M = Co (a), Ni (b), Cu (c), metal free (d)) 3a-3d without the methoxy group. The target Pc-C-60 dyads 3a-3d could be successfully synthesized in good yields also by Prato reaction. It is surprising for us that removal of a very small methoxy group from the big (OFbaC(60))PcCu(OCH3) molecule (2) significantly lowers the cp of (OFbaC(60))PcCu (3c) by about 70 degrees C in comparison with that of 2 having the methoxy group. Very interestingly, each of the novel dyads 3a-3d synthesized here shows perfect homeotropic alignment in the tetragonal columnar phase (Col(tet)). Moreover, it is noteworthy that 3c and 3d show only one Col(tet.o) mesophase having ordered stacking distance with perfect homeotropic alignment. Such simple phase transition can contribute to maintain stable performance in wide temperature range, when they will be applied to organic thin film solar cells.ArticleJOURNAL OF PORPHYRINS AND PHTHALOCYANINES. 17(4):264-282 (2013)journal articl

Discotic liquid crystals of transition metal complexes 49: establishment of helical structure of fullerene moieties in columnar mesophase of phthalocyanine-fullerene dyads

A homologous series of the phthalocyanine-fullerene dyads, C-n-PcM(OFbaC60) (n = 6, 8, 10, 12; M = Cu, Ni, Co: 3a-3f), have been synthesized to obtain homeotropic alignment at rt and investigate the effects of spacer chain length (n = 6, 8, 10, 12) and central metal (M = Cu, Ni, Co) on the mesomorphism. Interestingly, the shorter-spacer-substituted (n = 6, 8; M = Cu) dyads 3a and 3b showed a hexagonal columnar mesophase (Col(h)), whereas the longer-spacer-substituted (n = 10, 12; M = Cu, Ni, Co) dyads 3c-3f showed a tetragonal columnar mesophase (Col(tet)). Moreover, each of the homologs 3a-3e shows perfect homeotropic alignment in both the Col(h) and Col(tet) mesophases at rt. More interestingly, these columnar mesophases gave a very unique XRD reflection peak denoted as Peak H in a very small angle region of 0.8 < 2 theta < 2.0 degree. We have established at the first time from our developed two new XRD sample preparation techniques that the Peak H is due to the helical structure of fullerenes around columns formed by one-dimensionally stacked Pc cores. 1D nano array structure of donor and acceptor between two electrodes is recently proposed to obtain higher photoelectric conversion efficiency for organic thin film solar cells. This 1D nano array structure is almost compatible with the present homeotropically aligned Pc-C-60 dyads 3a-3f between two glass plates. Hence, these novel Pc-C-60 dyads 3a-3f may be very suitable to organic thin film solar cells.ArticleJOURNAL OF PORPHYRINS AND PHTHALOCYANINES. 17(11):1080-1093 (2013)journal articl