I suggest to add this, which I keep adding to my org-user-entities:
(("frac23" "\\frac23" t "⅔" "2/3" "⅔" "⅔")
("over" "\\over" t "/" "/" "/" "/")
("iff" "\\iff" t "⇔" "<=>" "<=>" "⇔")
("implies" "\\implies" t "⇒" "=>" "=>" "⇒"))The two first just allow to type simple fractions more readably, the two last add semantic variants to the already existing Rightarrow and Rightleftarrow.
