Discotic liquid crystals of transition metal complexes. Part 24 Synthesis and mesomorphism of porphyrin derivatives substituted with two or four bulky groups

Abstract

We have synthesized nine novel porphyrin derivatives, 1-8 and 1-Cu, substituted with various steric hindrance groups and long flexible chains in order to investigate the relationship between the molecular type of porphyrin derivatives and the resulting mesophase. Type 4 disc-like (C₁₂O)₁₆-TTPH₂ (1) and (C₁₂O)₁₆-TTPCu (1-Cu) derivatives exhibit D_h columnar mesophases, which are the first examples of meso-substituted porphyrin metal-free derivatives and copper complexes. Type 5 strip-like (C_nO)₈-BTPH₂ [4 (n=12), 5 (n=16)] derivatives having eight long chains at the 5,15-positions exhibit D_rd columnar mesophases. On the other hand, the type 5 (C₁₂O)₄-BTPH₂ (6) derivative having four long chains exhibits discotic lamellar D_L.rec1 and D_L.rec2 mesophases which have a two-dimensional rectangular structure within the layer. The (C₁₂O)₄-BPPH₂ (7) type 6 derivative also shows a D_L lamellar mesophase. Bruce et al. reported that type 3 rod-like porphyrin derivatives show calamitic mesophases of S_B, S_E and S_E′ phases. We revealed from these types of mesogenic porphyrin derivatives that such a successive change of the molecular structures causes their mesophases to change from discotic columnar to discotic lamellar, and further to calamitic.

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