The structure-reactivity relationships in metalation reactions of porphyrinoids have been studied using experimental and theoretical methods. A series of eight porphyrinoic ligands, derivatives of chlorophylls, was prepared in which both the peripheral groups and the degrees of saturation of the macrocycle were systematically varied. To reveal the solvent and structural factors which control the interactions of these macroligands with metal centers, their interactions with reactive Zn(2+) and inert Pt(2+) ions were investigated using absorption spectroscopy. In parallel, quantum chemical calculations (density functional theory, DFT) were performed for the same set of molecules to examine the influence of structural and electronic factors on the energy of the frontier orbitals, the nucleophilicity/electronegativity of the macrocycle, its hardness, and conformation. These static descriptors of chemical reactivity, relevant to metalation reactions, were verified against the results obtained in the experimental model. The experimentally obtained kinetic data clearly show that the solvent has a crucial role in the activation of the incoming metal center. In terms of chelator structure, the largest effects concern the size of the delocalized pi-electron system and the presence of side groups. Both the DFT calculations and experimental results show the strong influence of the macrocycle rigidity and of the peripheral groups on the chelating ability of porphyrinoids. In particular, the peripheral functionalization of the macrocyclic system seems to drastically reduce its reactivity toward metal ions. The effect of peripheral groups is two-fold: (i) a lower electron density on the core nitrogens, and (ii) increased rigidity of the macrocycle. The outcomes of the theoretical and experimental analyses are discussed also in terms of their relevance to the mechanism of biological metal insertion in the biosynthesis of heme and chlorophyll.

In the Ni-substituted chlorophylls, an ultrafast (<60 fs) deactivation channel is created, which is not present in Ni-porphyrins. This observation prompted us to investigate in detail the mechanism of excitation-to-heat conversion in Ni-substituted chlorophylls, experimentally, using time-resolved laser-induced optoacoustic spectroscopy, and theoretically, using group theory approach. The Ni-substituted chlorophylls show exceptional photostability and the optoacoustic measurements confirm the prompt and very efficient (100%) excitation-into-heat conversion in these complexes. Considering their excellent spectral properties and the loss-free excitation-into-heat conversion they are likely to become a new class of versatile photocalorimetric references. The curious features of the Ni-substituted chlorophylls originate from the symmetry of a ligand field created in the central cavity. The central N-Ni(2+) bonds, formed via the donation of two electrons from each of the sp(2) orbitals of two central nitrogens to an empty [Formula: see text] hybrid centered on Ni(2+), have a considerable covalent character. The extreme rate of excited state relaxation is then not due to a ladder of the metal centered d-states, often invoked in metalloporphyrins, but seems to result from a peculiar topology of the potential energy surface (a saddle-shaped crossing) due to the covalent character of the N-Ni(2+) bonds. This is confirmed by a strong 0→0 character of electronic transitions in these complexes indicating a similarity of their equilibrium geometries in the ground (S(0)) and the excited states (both Q(X) and Q(Y)). The excitation energy is very efficiently converted into molecular vibrations and dissipated as heat, involving the central Ni(2+). These Ni-substituted pigments pose a fine exemplification of symmetry control over properties of excited states of transition metal complexes.

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High pressure in combination with optical spectroscopy was used to gain insights into the interactions between Mg(2+), Zn(2+), and Ni(2+) ions and macrocyclic ligands of porphyrinoid type. In parallel, the central metal ion-macrocycle bonding was investigated using theoretical approaches. The symmetry properties of the orbitals participating in this bonding were analyzed, and pigment geometries and pressure/ligation effects were computed within DFT. Bacteriopheophytin a was applied as both a model chelator and a highly specific spectroscopic probe. The analysis of solvent and pressure effects on the spectral properties of the model Mg(2+), Zn(2+), and Ni(2+) complexes with bacteriopheophytin a shows that various chemical bonds are formed in the central pocket, depending on the valence configuration of the central metal ion. In addition, the character of this bonding depends on symmetry of the macrocyclic system. Since in most cases it is not coordinative bonding, these results challenge the conventional view of metal ion bonding in such complexes. In (labile) complexes with the main group metals, the metal ion-macrocycle interaction is mostly electrostatic. Significantly, water molecules are not preferred as a second axial ligand in such complexes, mainly due to the entropic constraints. The metal ions with a closed d shell may form (stable) complexes with the macrocycle via classical coordination bonds, engaging their p and s orbitals. Transition metals, due to the unfilled d shell, do form much more stable complexes, because of strong bonding via both coordination and covalent interactions. These conclusions are confirmed by DFT computations and theoretical considerations, which altogether provide the basis to propose a consistent and general mechanism of how the central metal ion and its interactions with the core nitrogens govern the physicochemical properties of metalloporphyrinoids.

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