  We explore time-resolved Coulomb explosion induced by intense, extreme
ultraviolet (XUV) femtosecond pulses from the FLASH free-electron laser as a
method to image photo-induced molecular dynamics in two molecules, iodomethane
and 2,6-difluoroiodobenzene. At an excitation wavelength of 267\,nm, the
dominant reaction pathway in both molecules is neutral dissociation via
cleavage of the carbon--iodine bond. This allows investigating the influence of
the molecular environment on the absorption of an intense, femtosecond XUV
pulse and the subsequent Coulomb explosion process. We find that the XUV probe
pulse induces local inner-shell ionization of atomic iodine in dissociating
iodomethane, in contrast to non-selective ionization of all photofragments in
difluoroiodobenzene. The results reveal evidence of electron transfer from
methyl and phenyl moieties to a multiply charged iodine ion. In addition,
indications for ultrafast charge rearrangement on the phenyl radical are found,
suggesting that time-resolved Coulomb explosion imaging is sensitive to the
localization of charge in extended molecules.
