Sitting-Atop metallo-porphyrin complexes: experimental and theoretical investigations on such elusive species.
The interaction between the sodium cation and two meso-aryl porphyrins (tetraphenylporphyrin, TPP, and tetra(4-methoxyphenyl)porphyrin, TMPP) leads to the formation of new species that have been identified as Sitting-Atop (SAT) complexes, where the metal ion interacts with the N atoms of the porphyrin core without the concomitant deprotonation of the N-H groups. These species have been attained in low polarity solvent through the interaction of the porphyrin free bases with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaTFPB), and investigated in situ through a combination of spectroscopic techniques, such as UV/vis absorption and fluorescence (static and time-resolved), resonance light scattering, FT-IR, and (1)H NMR. All spectroscopic evidence points to the occurrence of a single equilibrium between each parent compound and its SAT complex, ruling out the presence of other metallo-, protonated, or aggregated porphyrins in solution. The 1:1 stoichiometry of the adducts has been determined via continuous variation method (Job's plot), and an estimate of the corresponding association constants in CH(2)Cl(2) at 298 K have been obtained by UV/vis titration (K(eq) = (9 +/- 4) x 10(5) L mol(-1) and (5 +/- 2) x 10(6) L mol(-1) for TPP and TMPP, respectively). Density-functional theory (DFT) calculations on SAT model complexes, [NaTPP(PF(6))] and [NaTMPP(PF(6))], have provided information on the molecular structure of these elusive species and on the nature and strength of the sodium-porphyrin interaction. It is found that the sodium ion is bound to the four nitrogen atoms of the porphyrin core. The involvement of the pyrrolic N atoms results in a modest but not negligible elongation of the N-H bonds, pyramidalization of the hydrogen atoms, and blue shift of the N-H stretching frequencies. Electronic structure and energy decomposition analysis reveal that covalent interactions, mainly consisting of porphyrin to sodium charge transfer interactions, are an important component of the sodium-porphyrin bond. Time-dependent DFT (TDDFT) calculations of the lowest excited states of the model systems provide an unambiguous interpretation of the absorption and emission properties of the experimentally identified SAT complexes.
De Luca
Giovanna
G
Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Università di Messina, and C.I.R.C.M.S.B., Salita Sperone 31, Vill. S. Agata, Messina, Italy.
Romeo
Andrea
A
Scolaro
Luigi Monsù
LM
Ricciardi
Giampaolo
G
Rosa
Angela
A
D003198:Computer Simulation; D009682:Magnetic Resonance Spectroscopy; D008665:Metalloporphyrins / Q000737:chemistry*; D008956:Models, Chemical; D011166:Porphyrins / Q000737:chemistry*; D012964:Sodium / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared
D008665:Metalloporphyrins; D011166:Porphyrins; C409084:tetraphenylporphyrin; C021096:tetra(4-N-methylpyridyl)porphine; D012964:Sodium