cg401380a_si_001.pdf (2.97 MB)
Single Crystal to Single Crystal Polymerization of a Self-Assembled Diacetylene Macrocycle Affords Columnar Polydiacetylenes
journal contribution
posted on 2014-03-05, 00:00 authored by Weiwei
L. Xu, Mark D. Smith, Jeanette A. Krause, Andrew B. Greytak, Shuguo Ma, Cory M. Read, Linda S. ShimizuThis manuscript describes a single-crystal-to-single-crystal
polymerization
of the dihydrate of diacetylene 1 (1·2H2O) to give an unusual polydiacetylene (PDA) structure that
consists of aligned nanotubes, with each covalently bonded nanotube
having two parallel PDA chains that run parallel down opposite sides
of a channel defined by the macrocycle. Each PDA nanotube is connected
with four other columns via amide hydrogen bonds with an N-(H)···O
distance of 2.888(4) Å. Such well-ordered polymers should display
quasi-one-dimensional electronic structures and may be of interest
for the formation of highly conductive organic materials. We obtained
the 1·2H2O form in bulk, which was polymerized
by heating. Powder X-ray diffraction suggests that bulk PDA powder
is single phase and displays a similar structure as the PDA single
crystals. Furthermore, we showed that PDA crystals absorbed I2 vapor. We believe that this unique PDA structure, which is
amenable to property control via adsorbed guests, will be an attractive
one for investigating charge-transfer doping in PDA-based organic
electronic materials. We also observed two additional crystal forms,
including 1·MeOH, which also shows a columnar assembly,
and a tetrahydrate 1·4H2O that shows
water tetramers that link four cycles into a 2D sheet structure.