The bis(aryl)diacetylenes 1,4-bis(3-quinolyl)-1,3-butadiyne (1), 1,4-bis(4-isoquinolyl)-1,3-butadiyne (2), and 1,4-bis(3-pyridyl)-1,3-butadiyne (3) form strongly halogen bonded complexes with organic iodides, including tetraiodoethylene (TIE), 1,4-diiodotetrafluorobenzene (F4DIB), and 1,4-diiodooctafluorobutane (F8DIBut). The crystal structures for the new donor, 2, as well as for six complexes, 1·TIE, 1·F4DIB, 2·TIE, 2·F4DIB, 3·(F4DIB)2, and 3 2· (F8DIBut)2, are reported. Extended chain structures consisting of donor and acceptor molecules are observed in all cases, except that of 3 2·(F8DIBut)2, which forms a molecular adduct. In most cases, the complexes segregate into columns of donors and acceptors, as is typical for this class of complexes. However, 1·F4DIB displays an unusual “crosshatched” pattern with each acceptor directly above the diacetylene moiety of another donor along the b-axis. In addition to 1·F4DIB, 3 2·(F8DIBut)2 also exhibits packing that does not consist of segregated stacks (i.e., the acceptor in the chain sits on top of one end of the donor and the uncomplexed F4DIB sits on top of the other end). Neither diacetylene 2, nor any of the complexes, pack in a manner that would allow for topotactic polymerization of the diacetylene moiety.

Like 1,4-bis(3-quinolyl)buta-1,3-diyne, its structural isomer, 1,4-bis(4-isquinolyl)buta-1,3-diyne, undergoes both photo-and thermal polymerization. Thermal polymerization of each material leads to more amorphous, less thermally stable polymers than are observed in the respective photopolymerization. The diacetylenes are found to react with certain organoiodines to give N-I charge-transfer complexes. Thermolysis of the complexes evolves the organoiodine species prior to polymerization of the diacetylene. The complexes fail to polymerize upon photolysis.