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Hi Ash,
1) Well I wouldn't recommend using a DCDC buck converter to provide an ADC reference as the output voltage has some ripple due to the switching topology of the converter. It's recommended in order to get an ADC reference to use either external voltage references or use CC254x internal reference.
2) Concerning the power saving I would recommend to first supply your CC254x directly and measure the output current ( you can use a variable voltage supply and test different voltage from 2.1 to 3.4V for example), and then use the TPS62740 with a 2.1V output and vary your input voltage. You will see that the drawn current is decreased significantly using the buck converter. comparing to direct supply.
Also note that a battery's life is reduced when using higher current peaks even is the same amount of power is used.
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Amjad