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Fluorine is the most electronegative element because it is the most readily available to fill its octet and obtain a noble gas configuration because it has seven valence electrons; or if you will, it is the most "willing" to accept a single electron to fill its octet and the most "unwilling" to donate electrons to fill other octets.
Fluorine is the most electronegative element because it has 5 electrons in its 2P shell. Since is so close to noble gas configuration the electrons are held very close to the nucleus and its desire to gain an electron is very high.
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