1. Why does the 75MHz signal radiate and cause the issue where the 25MHz does not cause the failure in EMC?
DC/DC don't use sine wave which consists only one frequency, it uses square wave which consists of a sum of a large number of odd harmonics which are multiply of square wave frequency. It means that if you're using 25 MHz square wave it consists of 25 MHz sine + 25*3=75 MHz sine + 25*5=125 MHz sine + 25*7=175 MHz sine + 25*9=225 MHz sine + ...
And since square wave duty cycle may not be precise, it also may consists a lot of even harmonics (in your case 25*2=50 MHz + 25*4=100 MHz + 25*6=150 MHz + 25*8=200 MHz...)
Higher frequency has shorten wavelength, it means that it needs shorten wire to radiate and as result higher frequency is radiated more efficiently on wires.
Also, when you say, "Unbalanced trace" - do you mean "unterminated trace" ?
No. Unbalanced means that transmission line wires do not have symmetrical electrical characteristics relative to each other. For example, when one wire has different geometry in 3d space than second wire, another example when transmission line has two ground wires and one signal wire or vice versa. Coax cable for AC currents also unbalanced, because AC current flows on conductor surface, so coax cable actually has three wires for AC current - central conductor surface, inner braid surface and outer braid surface.
Such unbalanced transmission line may leads to common mode currents and as result may receive or radiate interference from/to environment, it may work like large coil of transformer, where all bodies around such line will be used as transformer core which will be used to couple your transmission line with other nearby electronic circuits.
Regarding to PCB, such PCB needs to use as small as possible high frequency loops and small conductor surface area used for RF currents. It needs to use proper ground geometry, blocking capacitors and inductors for filtering to block RF current flow through ground and other path.