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AsF3 has a higher boiling point than AsF5 because it has lone pairs that distort the geometry, therefore making the shape polar. But AsF5 is bigger, so does the dipole-dipole interaction have a greater influence in bond strength than the size of the molecule?
I think that in this case, since AsF3 is a polar molecule and AsF5 is a nonpolar molecule, the dipole-dipole attraction between AsF3 molecules are greater than the London Dispersion forces between AsF5 molecules, thus it is harder to break the bonds of AsF3 molecules, so the boiling point is higher.
Polarity plays a part in determining which structure has a higher boiling point. AsF3 has the higher boiling point because it is a polar molecule and thus has dipole-dipole interactions, while AsF5 is a nonpolar molecule with London dispersion forces. London dispersion forces are weaker than dipole-dipole interactions.
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