Crossed molecular beams experiments were conducted to investigate the chemical dynamics of the reaction of dicarbon molecules, C(2)(X(1)Sigma(g)(+)/a(3)Pi(u)), with diacetylene, C(4)H(2)(X(1)Sigma(g)(+)) at two collision energies of 12.1 and 32.8 kJ mol(-1). The dynamics were found to be indirect, involved C(6)H(2) intermediates, and were dictated by an initial addition of the dicarbon molecule to the carbon-carbon triple bond of diacetylene. The initial collision complexes could isomerize. On the singlet surface, the resulting linear triacetylene molecule (C(6)H(2)(X(1)Sigma(g)(+))) decomposed without an exit barrier to form the linear 1,3,5-hexatriynyl radical (C(6)H(X(2)Pi)). On the triplet surface, the dynamics suggested at least a tight exit transition state involved in the fragmentation of a triplet C(6)H(2) intermediate to yield the 1,3,5-hexatriynyl radical (C(6)H(X(2)Pi)) plus atomic hydrogen. On the basis of the experimental data, we recommend an experimentally determined enthalpy of formation of the 1,3,5-hexatriynyl radical of 1014 +/- 27 kJ mol(-1) at 0 K. Our experimental results and the derived reaction mechanisms gain full support from electronic structure calculations on the singlet and triplet C(6)H(2) potential-energy surfaces. The identification of the 1,3,5-hexatriynyl radical under single collision conditions implies that the neutral-neutral reaction of dicarbon with diacetylene can lead to the formation of 1,3,5-hexatriynyl radicals in the interstellar medium and possibly in the hydrocarbon-rich atmospheres of planets and their moons such as Saturn's satellite Titan.