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In this case, the molecular weight comparison is not as important. Even though AsF5 has stronger London dispersion forces than AsF3, the dipole-dipole interactions that AsF3 has are much stronger than any London dispersion forces. In general, you only need to focus on London dispersion forces and compare molecular weights when it's dealing with nonpolar molecules. If other types of intermolecular forces are present, you focus on those.
You would consider the weight if both molecules are not polar which is not the case here. AsF3 displays dipole-dipole interactions which indicates it's polar while AsF5 only displays LDF forces so it's not polar. Dipole-dipole is stronger than any LDF so AsF3 would have the higher boiling point.
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