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Yes, you could use to create inverting voltage. But need to remember that, in this application, the GND pin of TPS54339 is connected to FB-5V, which means that all the other pin is reference to FB-5V as GND. In this case, SS cap, VREG5 cap and EN pin should reference to F-5V not board ground. Please consider this in this kind of application. Other than that, please also put one or two input cap between Vin pin and GND (Fb-5V) pin of IC. Thanks!
