Fluorescence works with vibrational relaxation. The molecule first goes to vibrational sublevels, which are over the first excited state (LUMO). Then with vibrational relaxation, it goes to LUMO.
Then, comes the fluorescence itself, that is a deexitation via emission of a photon. This way the molecule goes back to ground state (HOMO).
Now the emitted photons this way always have a longer wavelength (smaller energy), then the absorbed ones.
When a molecule absorbs a photon of UV or visible light, an electron moves from the HOMO to the
LUMO to create either the excited state in its ground vibrational level, or the excited state vibrationally
excited. From the sublevels, it can undergo “vibrational relaxation”, which causes it to lose a little bit of
energy non-radiatively (that is, without emitting a photon), and drop back down to the ground state. Once
it reaches the lowest vibration level of the excited state, it can emit a photon and drop back to the ground
state or the ground state vibrationally excited, or it can decay back to ground state non-radiatively by
emission of heat.
You are asking whether certain materials will fluoresce only in response to certain wavelengths.
It is possible to do Molecular fluorescence spectrophotometry, and create certain materials that will only emit (fluoresce) if a certain wavelength photon excites their molecules.