Origin of Color of #pi#-Conjugaed Columnar Polymers. 1. Poly(p-3-methylbutoxy)phenylacetylene Prepared Using a [Rh(norbornadiene)Cl]_2 Catalyst

摘要

Stereoregular polymerization of (p-3-methylbutoxy)phenylacetylene (p3MBPA) was suc- cessfully performed with a [Rh(NBD)Cl]2 catalyst to afford poly(p-3-methylbutoxy)phenylacetylene (Pp3MBPA) having a cis-transoid form in high yields when ethanol or I-butanol in the presence of triethylamine was used as the polymerization solvent. The resulting cis polymer was composed of a pseudohexagonal structure called columnar as If-conjugated self-assembly or If-conjugated self-organization in the solid state. The columnar polymer underwent isomerization from the predominant cis to trans form when compressed at 100 kglcm2 at room temperature. T~e pristine polymer and the compressed polxmer were characterized in detail using lH NMR, wide-angle X-ray diffraction, laser Raman, electron spin resonance, and diffuse reflective UV -vis methods. Consequently, the data showed that the absorption maximum of the If-conjugated columnar polymer appears in an extremely longer wavelength region, i.e., at 490 nm, despite the cis form compared with 450 nm of the amorphous cis form. In the solid state, a large blue shift of the absorption maximum was found to be induced when the columnar structure was destroyed by compression to produce a trans-transoid form which has planar zigzag If-conjugation sequences. The pristine columnar polymer showed the J.max as an entire absorption at notably longer wavelength so that the chromophore of the If-conjugated columnar polymer is not to be simply attributed to the primary structure, e.g., a repeated double-single bond structure, but rather should be ascribed to that of aggregated molecules called the If-conjugated columnar as self-assembly or self-organization. This explanation is anew concept with respect to the color of If-conjugated columnar polymers and is very important for the molecular design of electroluminescense (EL) and nonlinear optical (NLO) materials which are used at present in the solid state.