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)
3
Cl or Mn(2,2′-bipy-5,5′-dicarboxylic acid)(CO)
3
Br with LiCl or LiBr, respectively, produces single crystals of {Li
2
(DMF)
2
[(2,2′-bipy-5,5′-dicarboxylate)Re(CO)
3
Cl]}
n
(
ReLi
) or {Li
2
(DMF)
2
[(2,2′-bipy-5,5′-dicarboxylate)Mn(CO)
3
Br]}
n
(
MnLi
). 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)
3
Cl (
ReLi
) or Mn(2,2′-bipy-5,5′- dicarboxylate)(CO)
3
Br (
MnLi
). The photophysical and photochemical behaviour of both
ReLi
and
MnLi
are probed. The rhenium-containing MOF,
ReLi
, exhibits luminescence and the excited state behaviour, as established by time-resolved infrared measurements, is closer in behaviour to that of unsubstituted [Re(bipy)(CO)
3
Cl] rather than a related MOF where the Li(I) cations are replaced by Mn(II) cations. These observations are further supported by density functional theory calculations. Upon excitation
MnLi
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.
This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.
Time-Resolved In Situ Diffraction Study of the Solvothermal Crystallization of Some Prototypical Metal-Organic Frameworks
