Despite the many advances in the design of porphyrin derivatives for Langmuir Blodgett (LB) films, the formation of compressible monolayers with a flat-on orientation of the macrocycle has remained elusive. Presented here is the synthesis of tetraazaporphyrins (TAPs) that contain different types of functional groups to enhance their amphiphilic properties and stabilize their face-on orientation at the air-water interface. Some of these compounds also display self-organization in their bulk phase. The new design of these TAPs combines several structural features of TAPs we previously reported, which contain eight identical side-chains with terminal carboxylic acid, azide, and acetylene groups.^1,2 Attachement of both carboxylic acid and azide or acetylene groups generated TAPs that form stable Langmuir and LB monolayers with flat-on orientation of the macrocycle. We also succeeded in cross-linking these Langmuir and LB monolayers via cycloaddition of azide and acetylene groups (click chemistry) in the presence Cu catalyst and thermally.

1. M. M. Ahmida, S. Dufour, Hui–Sheng Li, H. Kayal, R. Schmidt, C. E. DeWolf and S. H. Eichhorn, 2013, Soft Matter (9,3) 811-9, DOI:10.1039/c2sm27064a.

2. Himadri Kayal, M. M. Ahmida, S. Dufour, H. Taing, and S. H. Eichhorn, 2013, J. Mater. Chem. C, (1,42) 7064-7072, DOI: 10.1039/C3TC31588F.