Yes, it is undefined behaviour.
ISO/IEC 9899:1999 6.5.7 Bitwise shift operators ΒΆ3
The integer promotions are performed on each of the operands. The type of the result is that of the promoted left operand. If the value of the right operand is negative or is greater than or equal to the width of the promoted left operand, the behavior is undefined.
C11 aka ISO/IEC 9899:2011 says the same.
You should first cast b to the target integer type. Another point is that you should put parentheses around the macro parameters to avoid surprises by operator precedences. Additionally, the comma operator is very useful here, allowing you to avoid the braces, so that the macro can be used as a normal command, closed with a semicolon.
#define splitup(a,b,c) ( (b) = (a) >> 32, (c) = (a) & 0xffffffff )
#define combine(a,b,c) ( (a) = ((unsigned long long)(b) << 32) | (c) )
Additional casts may be necessary for `splitup to silence warnings about precision loss by over-paranoid compilers.
#define splitup(a,b,c) ( (b) = (unsigned long)((a) >> 32), (c) = (unsigned long)((a) & 0xffffffff) )
And please don’t even think about using your self-written encryption for production code.