Crystallography has seen a continuous expansion into more specialised areas driven by advancements in instrumentation. There are two fields of particular interest; charge-density and photo-crystallography, both of which have significantly benefited from technological progress, such as improved detectors and higher-efficiency, higher-energy LEDs. Each of these fields individually pose substantial challenges in order to produce interesting data. Combining these techniques introduces another level of complexity but with a substantial benefit, direct observation of excited-state molecular orbitals. A set of transition-metal complexes were synthesised with this aim in mind, and were chosen to overcome the limitations imposed by both of these techniques.