RESUMO
A combined experimental and theoretical study is presented of several ligand addition reactions of the triplet fragment 3CpMn(CO)2 formed upon photolysis of CpMn(CO)3. Experimental data are provided for reactions in n-heptane and perfluoromethylcyclohexane (PFMCH), as well as in PFMCH doped with C2H6, Xe and CO2. In PFMCH we find that the conversion of 3CpMn(CO)2 to 1CpMn(CO)2(PFMCH) is much slower (τ = 18 (±3) ns) than the corresponding reactions in conventional alkanes (τ = 111 (±10) ps). We measure the effect of the coordination ability by doping PFMCH with alkane, Xe and CO2; these doped ligands form the corresponding singlet adducts with significantly variable formation rates. The reactivity as measured by the addition timescale follows the order 1CpMn(CO)2(C5H10) (τ = 270 (±10) ps) > 1CpMn(CO)2Xe (τ = 3.9 (±0.4) ns) â¼ 1CpMn(CO)2(CO2) (τ = 4.7 (±0.5) ns) > 1CpMn(CO)2(C7F14) (τ = 18 (±3) ns). Electronic structure theory calculations of the singlet and triplet potential energy surfaces and of their intersections, together with non-adiabatic statistical rate theory, reproduce the observed rates semi-quantitatively. It is shown that triplet adducts of the ligand and 3CpMn(CO)2 play a role in the kinetics, and account for the variable timescales observed experimentally.
RESUMO
Ferrous iron(II) hexacyanide in aqueous solutions is known to undergo photoionization and photoaquation reactions depending on the excitation wavelength. To investigate this wavelength dependence, we implemented ultrafast two-dimensional UV transient absorption spectroscopy, covering a range from 280 to 370 nm in both excitation and probing, along with UV pump/visible probe or time-resolved infrared (TRIR) transient absorption spectroscopy and density functional theory (DFT) calculations. As far as photoaquation is concerned, we find that excitation of the molecule leads to ultrafast intramolecular relaxation to the lowest triplet state of the [Fe(CN)6]4- complex, followed by its dissociation into CN- and [Fe(CN)5]3- fragments and partial geminate recombination, all within <0.5 ps. The subsequent time evolution is associated with the [Fe(CN)5]3- fragment going from a triplet square pyramidal geometry, to the lowest triplet trigonal bipyramidal state in 3-4 ps. This is the precursor to aquation, which occurs in â¼20 ps in H2O and D2O solutions, forming the [Fe(CN)5(H2O/D2O)]3- species, although some aquation also occurs during the 3-4 ps time scale. The aquated complex is observed to be stable up to the microsecond time scale. For excitation below 310 nm, the dominant channel is photooxidation with a minor aquation channel. The photoaquation reaction shows no excitation wavelength dependence up to 310 nm, that is, it reflects a Kasha Rule behavior. In contrast, the photooxidation yield increases with decreasing excitation wavelength. The various intermediates that appear in the TRIR experiments are identified with the help of DFT calculations. These results provide a clear example of the energy dependence of various reactive pathways and of the role of spin-states in the reactivity of metal complexes.
RESUMO
In contrast to the ground state, the calculation of the infrared (IR) spectroscopy of molecular singlet excited states represents a substantial challenge. Here, we use the structural IR fingerprint of the singlet excited states of a range of coumarin dyes to assess the accuracy of density functional theory based methods for the calculation of excited state IR spectroscopy. It is shown that excited state Kohn-Sham density functional theory provides a high level of accuracy and represents an alternative approach to time-dependent density functional theory for simulating the IR spectroscopy of singlet excited states.
RESUMO
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.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.