Abstract1‐Alkynes containing azobenzene mesogenic moieties [HCC(CH2)9O phNNphOR; R = ethyl (1), octyl (2), decyl (3), (S)‐2‐methylbutyl (4), or (S)‐1‐ethoxy‐1‐oxopropan‐2‐yl (5); ph = 1,4‐phenyl] were synthesized and polymerized in the presence of a Rh catalyst {(nbd)Rh+[B(C6H5)4]−; nbd = 2,5‐norbornadiene} to yield a series of liquid‐crystalline polymers in high yields (e.g., >75%). These polymers had moderate molecular weights (number‐average molecular weight ≥ 12,000), high cis contents in the main chain (up to 83%), good thermal stability, and good solubility in common organic solvents, such as tetrahydrofuran, chloroform, and dichloromethane. These polymers were thoroughly characterized by a combination of infrared, nuclear magnetic resonance, thermogravimetric analysis, differential scanning calorimetry, polarized optical microscopy, and two‐dimensional wide‐angle X‐ray diffraction techniques. The liquid‐crystalline behavior of these polymers was dependent on the tail group attached to the azobenzene structure. Poly‐1, which had the shortest tail group, that is, an ethyl group, showed a smectic A mesophase, whereas poly‐2, poly‐3, and poly‐5, which had longer or chiral tail groups, formed smectic C mesophases, and poly‐4, which had another chiral group attached to the azobenzene structure, showed a chiral smectic C mesophase in both the heating and cooling processes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4532–4545, 2006
