Okay, I see what you mean. Although, if zero is an eigenvalue then the rank of A is (N-1) : where N is the number rows/columns. But one of the requirements for doing a eigenvalue decomposition is that the rank is full and that the rows/columns are linearly independent.
We take a simple example:
A = [-a,a;b,-b]. In this example, the top row is (b/a) *bottom row, so there is linear dependence. I'm sure that this is true for the other cases (more rows/columns). Because of this, I don't see how the decomposition could be reliable.
------------------
Now, to try your example, (this was a print out from the MATLAB environment):
First off, the expressions don't even commute
>> inv(U)*[1,0;0,exp(7)]*U
ans =
157.5190 -469.5571
-313.0380 940.1141
>> U*[1,0;0,exp(7)]*inv(U)
ans =
157.5190 313.0380
469.5571 940.1141>> U
U =
2 1
-1 3
>> A=[1,2;3,6]
A =
1 2
3 6
>> exp(A)
ans =
2.7183 7.3891
20.0855 403.4288
So unfortunately, it does not work.
<br />
exp(A) ≠\frac{1}{7} \, \left(\begin{array}{cc}<br />
2 & 1 \\ -1 & 3 \end{array}\right)<br />
<br />
\cdot \left(\begin{array}{cc}<br />
e^0 & 0 \\ 0 & e^7 \end{array}\right)<br />
<br />
\cdot \left(\begin{array}{cc}<br />
3 & -1 \\ 1 & 2 \end{array}\right)<br />