Complex structures of warm and hot dense matter are essential to understanding the behavior of materials in high energy density processes and provide new features of matter constitutions. Here, around a new unified first-principles determined Hugoniot curve of iron from the normal condensed condition up to 1 Gbar, the novel structures characterized by the ionic clusters with electron bubbles are found using quantum Langevin molecular dynamics. Subsistence of complex clusters can persist in the time scale of 50 fs dynamically with quantum flowing bubbles, which are produced by the interplay of Fermi electron degeneracy, the ionic coupling, and the dynamical nature. With the inclusion of those complicated features in quantum Langevin molecular dynamics, the present equation of states could serve as a first-principles based database in a wide range of temperatures and densities.