Photophysical Analysis of 1,10-Phenanthroline-Embedded Porphyrin Analogues and Their Magnesium(II) Complexes

The synthesis, characterization, photophysical properties, and theoretical analysis of a series of tetraaza porphyrin analogues (H?Pn: n=14) containing a dipyrrin subunit and an embedded 1,10-phenanthroline subunit are described. The meso-phenyl-substituted derivative (H?P1) interacts with a Mg2+ salt (e.g., MgCl2, MgBr2, MgI2, Mg(ClO4)2, and Mg(OAc)2) in MeCN solution, thereby giving rise to a cation-dependent red-shift in both the absorbance- and emission maxima. In this system, as well as in the other H?Pn porphyrin analogues used in this study, the four nitrogen atoms of the ligand interact with the bound magnesium cation to form Mg2+dipyrrinphenanthroline complexes of the general structure MgX?Pn (X=counteranion). Both single-crystal X-ray diffraction analysis of the corresponding zinc-chloride derivative (ZnCl?P1) and fluorescence spectroscopy of the Mg-adducts that are formed from various metal salts provide support for the conclusion that, in complexes such as MgCl?P1, a distorted square-pyramidal geometry persists about the metal cation wherein a chloride anion acts as an axial counteranion. Several analogues (H?Pn) that contain electron-donating and/or electron-withdrawing dipyrrin moieties were prepared in an effort to understand the structureproperty relationships and the photophysical attributes of these Mgdipyrrin complexes. Analysis of various MgX?Pn (X=anion) systems revealed significant substitution effects on their chemical, electrochemical, and photophysical properties, as well as on the Mg2+-cation affinities. The fluorescence properties of MgCl?Pn reflected the effect of donor-excited photoinduced electron transfer (d-PET) processes from the dipyrrin subunit (as a donor site) to the 1,10-phenanthroline acceptor subunit. The proposed d-PET process was analyzed by electron paramagnetic resonance (EPR) spectroscopy and by femtosecond transient absorption (TA) spectroscopy, as well as by theoretical DFT calculations. Taken together, these studies provide support for the suggestion that a radical species is produced as the result of an intramolecular charge-transfer process, following photoexcitation. These photophysical effects, combined with a mixed dipyrrinphenanthroline structure that is capable of effective Mg2+-cation complexation, lead us to suggest that porphyrin-inspired systems, such as H?Pn, have a role to play as magnesium-cation sensors.