JPEG, PNG, TGA, PDF changes hex color from PSD

I work for a company where the CEO is very into brand colors. He has the hex values of all the branded colors memorized. One of the branded colors is blue ( hex: 0039a6 ). Obviously, if he looks at my psd and samples a the color, it will display 0039a6.
However, whenever I save it out as a: jpg, tga, png, or pdf, the color's hex value will change to 1f419b. If he samples from one of those files, crisis! Wrong branded color!
I've made 2 layers and filled with with both colors and as far as I can tell, they are exactly the same to the eye, even if they're overlapping. So I just want to know why this happens so I can explain myself if he ever runs over to my desk.
Thanks!

Oh right, this is happening with Photoshop and Illustrator, which is why is didn't post on an individual programs forums. I forgot to add that to my previous post. Do you recommend that I post in both the Photoshop and Illustrator sections?
Edit: I did more tests. If I use the branded color 0039a6 in Illustrator and save it out as a png, tga, jpeg, pdf, and I then open one of those exported files in Photoshop, the hex value has changed.
If I use the branded color in Photoshop, exporting a png keeps the color as the correct hex value. JPG doesn't, which makes sense due to compression. So now the question is, why are the files I'm exporting from Illustrator and opening in Photoshop showing different hex values. You would assume that the pngs should be okay from both Photoshop and Illustrator?

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