I thought the defogger used the A/C to first dehumidify the air, then the heater core is used to heat the air. The result is dry hot air being blow at the windshield.
I know on my Civic, which has a separate button for the A/C compressor, does a rather lousy job clearing the windshield in defog mode with the A/C off, but quickly clears the windshield if I then turn the A/C on.