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These two series of trinuclear complexes show distinctly different photophysical and electrochemical properties. The <jats:bold>L2<\/jats:bold>\u2010bridged complexes exhibit strong luminescence and relatively long emission lifetimes in room\u2010temperature solution, which are typical of decay from <jats:sup>3<\/jats:sup>MLCT excited states, whereas <jats:bold>L1<\/jats:bold>\u2010bridged complexes show only very weak luminescence and short lifetimes under the same experimental conditions. The prominent differences in photophysical behavior between these two groups of trinuclear complexes has been rationalized by energy gap law, which has been supported by detailed analysis of the steady state and time\u2010resolved luminescence of these complexes. 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