As I read the question, you want find certain pairs $(a,b)$ to use the linear form $ax+by$ to represent positively only certain numbers, and only in a certain way. In particular, for any $n$ with $a,b<n<g(a,b)=ab-a-b$, it is either not representable as $ax+by$ for integers $x$ and $y$ where both $x$ and $y$ is at least $1$, or $n$ is representable and at most one of its maximal divisors is also representable.
Well, you aren't going to find many such $a,b$. Let's pick $s=a+b$. Then $2s, 3s, 6s$ are also representable, so by your condition $6s \gt ab -a -b$, or $7(a+b)>ab$. So the smaller of $a$ and $b$ is less than $14$, and as $b$ gets large $a$ is bounded above by $7$. And we haven't explored what happens when you pick $\lceil b/a \rceil a$. I predict there will be only finitely many such pairs.
Edit 2015.12.02: I don't see why there is so much difficulty. I shall attempt a very clear explanation.
Suppose $7(a+b)\leq ab$. Then $6(a+b) \leq ab -a -b$. Also $6(a+b), 3(a+b)$, and $2(a+b)$ are representable. Thus $(a,b)$ is not an excellent pair. Thus a pair is excellent implies $7(a+b) \gt ab$, which gives a bound on the smaller of $a$ and $b$, namely if $a$ is smaller then $14 \gt 7(1 + a/b) \gt a$. When $a$ is fixed and not too small $7a/(a-7) \gt b$. The remaining excellent pairs must have the smaller number at most 7. When the smaller number is 2 or 3, one can choose a larger coprime number to get an excellent pair. This happens because the interval of representability is too small for the condition to fail. I leave the cases 4 through 7 to the interested reader. End Edit 2015.12.02.
Gerhard "Leaving The Rest To You" Paseman, 2015.12.01