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In the 21st century, there were at least four Earth colonies here, presumably on its moons, such as Triton or Nereid. The extrasolar colony of Xartheb was founded by settlers from Neptune Colony IV. (Orion Press: "Alis Volat Propriis")
During the Dominion War the Starfleet Third Fleet established an outer defense perimeter at Neptune. During the Breen Attack on Earth the Breen fleet was able launch a surprise attack on the perimeter thanks to their cloaking devices before the Third Fleet could defend itself. (The Dominion War Sourcebook: The Fires of Armageddon)