You will want to use a generating function. For pennies, we can have $1, 2, ..., $ selections. So we have the generating function $f_{1}(x) = 1 + x + x^{2} + ... = \frac{1}{1-x}$. Similarly, with two-cent pieces, we have $f_{2}(x) = 1 + x^{2} + x^{4} + ... = \sum_{i=0}^{\infty} x^{2i} = \frac{1}{1-x^{2}}$. We continue this pattern to get the generating function:
$$f(x) = \frac{1}{1-x} \cdot \frac{1}{1-x^{2}} \cdot \frac{1}{1-x^{5}} \cdot \frac{1}{1-x^{10}} \cdot \frac{1}{1-x^{20}} \cdot \frac{1}{1-x^{50}}$$
You then would want to use something like a computer algebra system to expand out searching for the coefficient of $x^{100}$. Of course, you could theoretically do it by hand, but it would be tedious to do.
Edit: Generating functions work by using a formal geometric series to index terms. So $x^{0}$ says you have none of that term while $x^{53}$ says you have $53$ units. I am using them here to count the number of each coin. Pennies count one unit each, so $f_{1}(x) = \sum_{i=0}^{\infty} x^{i}$ counts the number of pennies you have. In contrast, the five cent pieces count as five units of money. So we have: $f_{5}(x) = \sum_{i=0}^{\infty} x^{5i}$.
By rule of product, we multiply each function together to get the main generating function. We then use geometric series identities to expand out the terms and seek the coefficient of $x^{100}$, which is your desired monetary amount.
This article provides a good look at generating functions too, at least to help conceptualize for you: http://www.dreamincode.net/forums/topic/304589-a-look-at-the-knapsack-problem-with-generating-functions/