Oliver and Laurel watch Lance's press conference about the new low level of crime in Starling City in episode #301 "The Calm".
Barry fights the Reverse-Flash outside the building in episode #109 "The Man in the Yellow Suit". The crew loads up their prisoners into the transport truck, and later Barry and others battle Wells outside the building in episode #122 "Rogue Air". Caitlin and Ronnie get married by Dr. Stein outside the building in episode #123 "Fast Enough".
Etta and Simon sneak Walter into Manhattan through this mass transit station in episode #419 "Letters of Transit".