956428-30-1Relevant articles and documents
Structurally homologous β- and meso-alkynyl amidinium porphyrins
Rosenthal, Joel,Young, Elizabeth R.,Nocera, Daniel G.
, p. 8668 - 8675 (2008/10/09)
Alkynylamidinium groups have been introduced at the β and meso positions of a nickel(II) porphyrin (PNi(II)) framework. The modification permits the distance between the amidinium-amidine acid-base group and porphyrin to be increased while effectively maintaining π conjugation between the porphyrin macrocycle and the acid-base functionality. Use of an ethynyl spacer as a linker (i) extends the amidinium functionality away from the sterically bulky mesityl groups of the porphyrin, allowing it to be nearly planar with respect to the porphyrin ring, and (ii) draws the π-orbital character of the porphyrin out toward the amidinium functionality, thereby engendering sensitivity of the electronic properties of the porphyrin macrocycle to the protonation state of the amidinium. The barrier for rotation of the amidinium group, as calculated by time-dependent density functional theory (TDDFT), is ～8.5kT (5 kcal/mol) for both porphyrins. Analysis of UV-visible absorption profiles for the β- and meso-alkynylamidinium PNi(II) upon deprotonation enables accurate determination of the amidinium acidity constants for the ground state (pKa(β) = 7.03 ± 0.1, pKa(meso) = 7.74 ± 0.1 in CH3CN) and excited state (pKa *(β) = 6.89 ± 0.1, pKa*(meso) = 8.37 ± 0.1 in CH3CN) porphyrins. Whereas pKa* a for the β-alkynylamidinium porphyrin, pKa* > pKa for the meso-alkynylamidinium porphyrin, indicating that β-alkynylamidinium PNi(II) is a photoacid and meso-alkynylamidinium PNi(II) is a photobase. These divergent behaviors are supported by analysis of the frontier molecular orbitals of the homologous pair with TDDFT.
