Solid State Polymerization of Diacetylenes with Amide Groups

Abstract

Two diacetylene derivatives (1, 2) carrying amide groups were prepared in order to control their packing arrangements by intermolecular hydrogen bonds. 1, 6-Bis(4-acetamidomethylphenoxy)-2,4-hexadiyne 1 is a symmetric diamide, which showed no changes by annealing. p-N-acetyl(6-hydroxy-2,4-hexadiynenyloxy)benzylamine 2 with amide and alcohol groups showed photo and thermal reactivity. Compound 2 crystallized in the monoclinic P2 1 =c space group with a ¼ 17.9162(3) Å , b ¼ 4.8646(2) Å , c ¼ 16.106(3) Å , b ¼ 105.19(1) . The molecules stacked onedimensionally along the b axis and the intermolecular hydrogen bonds of the amide groups ran along the stacking axis. The hydroxyl group in the other end of the structure of 2 was also involved in polymeric hydrogen bonds, which also appear to play an important role in the molecular arrangement.

Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

“…The diyne systems are parallel as requested; nevertheless, the angle of the reactive carbons and mostly their distance separations are not favorable, being distorted and much too long, respectively (Figure 4). Topochemical polymerization of diacetylene is also prevented because there is no long range parallel stacking of diynes [58][59][60][61][62][63][64][65][66][67]. …”

Estructura Molecular y Cristalina de un Derivado Diacetilénico: Octa-3,5-diino-1,8-diil-Bis( Octilcarbamato)

“…La estructura molecular refinada es la esperada, con una unidad asimétrica conformada por una media molécula (Figura 1). El enlace acetilénico C1C2 presenta la longitud esperada, 1.174 (11) A, y el ángulo de enlace C2Cl-Cl; está cercano a los 180º (simetria i: 4-x, -3-y, 1-z). La longitud del enlace central C 1-C 1; es corta, 1.3 82(18) A, pero similar a lo observado en otros compuestos diacetilénicos [22][23][24].…”

Rapid Access to Polychlorodiacetylene Single Crystals through H-Bond Templating and Computations on Helical PDA Oligomers

“…Indeed, alignment of DA monomer in the single crystal state can be achieved by various strategies, including the utilization of side chain groups involved in noncovalent interactions (Figure b), such as π stacking interactions , or hydrogen bonding interactions. − This latest example often stacks the DA units in reactive positions using urethane group − or amide group. − …”