TY - JOUR
T1 - Photochemistry of framework-supported M(diimine)(CO) 3 X complexes in three-dimensional lithium carboxylate metal–organic frameworks: monitoring the effect of framework cations
AU - Reade, Thomas J.
AU - Calladine, James A.
AU - Horvath, Raphael
AU - Greetham, Gregory M.
AU - Towrie, Michael
AU - Lewis, William
AU - Champness, Neil R.
PY - 2017/1/13
Y1 - 2017/1/13
N2 - 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)3Cl or Mn(2,2′-bipy-5,5′-dicarboxylic acid)(CO)3Br with LiCl or LiBr, respectively, produces single crystals of {Li2(DMF)2 [(2,2′-bipy-5,5′-dicarboxylate)Re(CO)3Cl]}n (ReLi) or {Li2(DMF)2[(2,2′-bipy-5,5′-dicarboxylate)Mn(CO)3Br]}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)3Cl (ReLi) or Mn(2,2′-bipy-5,5′- dicarboxylate)(CO)3Br (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)3Cl] 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.
AB - 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)3Cl or Mn(2,2′-bipy-5,5′-dicarboxylic acid)(CO)3Br with LiCl or LiBr, respectively, produces single crystals of {Li2(DMF)2 [(2,2′-bipy-5,5′-dicarboxylate)Re(CO)3Cl]}n (ReLi) or {Li2(DMF)2[(2,2′-bipy-5,5′-dicarboxylate)Mn(CO)3Br]}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)3Cl (ReLi) or Mn(2,2′-bipy-5,5′- dicarboxylate)(CO)3Br (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)3Cl] 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.
UR - https://doi.org/10.1098/rsta.2016.0033
U2 - 10.1098/rsta.2016.0033
DO - 10.1098/rsta.2016.0033
M3 - Article
SN - 0962-8428
VL - 375
JO - Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
JF - Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
IS - 2084
ER -