Correct if you design for 85C max at max Ta
Double-edge issue.. Too high is bad, too low from Temp is bad.
again I believe but you verify,, -200mV/60'C rise anything more is poor cooling in my books, we never allowed any hotspot>85C for commercial design
I guess you have already considered dumping your PWM and just buy a CC PSU for LEDs
Test Engineers had originally used Ta=Tc=25'C in semiconductor spec sheets, with massive controlled temp heat-sinks , then simply Ta=25 for pulse mode tests, (which you can't do for a uC.) How they do is up to them.
But we rarely know the Rjc of the LED package. A good clue is the Mfg Spec or Power vs Ta slope which is effectively the Rjc of the part, which is upwards of >500 deg C/W in 5mm Leds due to epoxy being a thermal insulator.
on another tangent... Sinkpad thermal solutions are pretty good for MCPCB.