title: Free base and metal complexes of 5,15-diaza-10,20-dimesitylporphyrins: synthesis, structures, optical and electrochemical properties, and aromaticities.
abstract: The synthesis, structures, optical and electrochemical properties, and aromaticity of a series of 5,15-diaza-10,20-dimesitylporphyrins (M-DAP; M = Pb, H(2), Ni, Pd, Pt, Zn; mesityl = 2,4,6-trimethylphenyl) are reported. Treatment of mesityl-substituted bis(5,5'-dibromodipyrrin) with sodium azide in the presence of lead(II) acetylacetonate afforded Pb-DAP, which was quantitatively converted to H(2)-DAP by acidolysis. The free base H(2)-DAP reacted with palladium(II), platinum(II), and zinc(II) salts to give Pd-DAP, Pt-DAP, and Zn-DAP, respectively. The crystal structures, optical and electrochemical properties, and aromaticities of these β-unsubstituted M-DAPs were comprehensively investigated by X-ray crystallography, UV-vis absorption/fluorescence spectroscopy, nanosecond flash photolysis, cyclic and differential pulse voltammetry, NMR spectroscopy, and density functional theory calculations. The obtained data show that  replacement of the 5- and 15-methine carbons with nitrogen atoms alters the intrinsic properties of the porphyrin 18π system as follows: (i) the coordination spheres at the N(4) core become contracted while keeping high planarity; (ii) the Q bands are red shifted and largely intensified; (iii) the electron-accepting ability is enhanced, whereas the electron-donating ability is reduced; (iv) the radiative decay rates from the S(1) state are enhanced; and (v) the aromaticity of the 18π circuit is slightly reduced in terms of both geometric and magnetic criteria. These optical and electrochemical properties of M-DAPs stem from their characteristic frontier orbitals; two HOMOs and two LUMOs are nondegenerate as a result of the incorporation of the electronegative nitrogen atoms at the two meso positions. In addition, the group 10 metals incorporated at the core finely tune the fundamental properties of DAP π systems through inductive effects as well as dπ-pπ antibonding orbital interactions; the HOMO-LUMO gaps of the group 10 metal complexes increase in the order Ni-DAP < Pd-DAP < Pt-DAP.
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan. matano@scl.kyoto-u.ac.jp
authors.forename: Yoshihiro
authors.initials: Y
authors.lastname: Matano
authors.forename: Tarou
authors.initials: T
authors.lastname: Shibano
authors.forename: Haruyuki
authors.initials: H
authors.lastname: Nakano
authors.forename: Yoshifumi
authors.initials: Y
authors.lastname: Kimura
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Imahori
mesh_terms: D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D008958:Models, Molecular; D015394:Molecular Structure; D055620:Optical Phenomena; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D010984:Platinum / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D011166:Porphyrins; D010984:Platinum; D010165:Palladium; D015032:Zinc