The Supplementary Material contains additional figures of X-ray structures from Photochemistry of framework-supported M(diimine)(CO)<sub>3</sub>X complexes in three-dimensional lithium-carboxylate metal-organic frameworks: monitoring the effect of framework cations

The structures and photochemical behaviour of two new metal-organic frameworks (MOFs) are reported. Reaction of Re(2,2'-bipy'-5,5'-dicarboxylic acid)(CO)<sub>3</sub>Cl or Mn(2,2'-bipy'-5,5'-dicarboxylic acid)(CO)<sub>3</sub>Br with either LiCl or LiBr, respectively, produces single crystals of {Li<sub>2</sub>(DMF)<sub>2</sub> [(2,2'-bipy'-5,5'-dicarboxylate)Re(CO)<sub>3</sub>Cl]}<sub>n</sub> (<b>ReLi</b>) or {Li<sub>2</sub>(DMF)<sub>2</sub>[(2,2'-bipy'-5,5'-dicarboxylate)Mn(CO)<sub>3</sub>Br]}<sub>n</sub> (<b>MnLi</b>). The structures formed by the two MOFs comprise one-dimensional chains of carboxylate-bridged Li(I) cations that are cross-linked by units of Re(2,2'-bipy'-5,5'-dicarboxylate)(CO)<sub>3</sub>Cl (<b>ReLi</b>) or Mn(2,2'-bipy'-5,5'- dicarboxylate)(CO)<sub>3</sub>Br (<b>MnLi</b>). The photophysical and photochemical behaviour of both <b>ReLi</b> and <b>MnLi</b> are probed. The rhenium-containing MOF, <b>ReLi</b>, exhibits luminescence and the excited state behaviour, as established by time-resolved infrared measurements, are closer in behaviour to that of unsubstituted [Re(bipy)(CO)<sub>3</sub>Cl] rather than a related MOF where the Li(I) cations are replaced by Mn(II) cations. These observations are further supported by DFT calculations. Upon excitation <b>MnLi</b> forms a dicarbonyl species which rapidly recombines with the dissociated CO, in a fashion consistent with the majority of the photoejected CO not escaping the MOF channels.