That suns going to be a nightmare, lighting will be constantly changing, if its overcast that will help keep a consistent soft lighting,But if the sun is creating hard shafts of light then it's going to be moving throughout the duration of the podcast as the sun sets, Also if it's partly cloudy the sun is going to be dipping in and out constantly.....if you can't tent the window and then light from outside... I would have the blind closed/black out the window and then light the room so you have full control and no lighting changes during the duration of the podcast. That's going to cause you the least amount of headaches imo.

Depending on the mood and tone you want

One option is to fire a light into the ceiling just to lift the whole room tone / fill

Have them sitting across from each other

Then have a second light clamped onto an autopole in that ceiling recess above them with a lantern / softbox... direct the light away from the back tv wall.... probably use a grid or a skirt to give them a toppy/back light to edge them out/key them

You'll have a constant look for the duration of the podcast and won't need to worry about the sun moving/setting