Self-assembly of a porphyrin array via the molecular recognition approach: synthesis and properties of a cyclic zinc(II) porphyrin trimer based on coordination and hydrogen bonding.
Self-assembly of [5-(pyrazol-4-yl)-10,20-bis(p-tolyl)-15- (2-ethoxycarbonylphenyl)porphyrinato]-zinc(II) (1), designed to have both a coordination site and a hydrogen bonding site, leads to a stable cyclic trimer array where coordination of the pyrazole nitrogen to the zinc(II) ion as well as hydrogen bonding between carbonyl oxygen and pyrazole NH holds each zinc(II) porphyrin. The recognition event for pyrazole has been confirmed preliminarily in the model studies using [5-(2-ethoxycarbonylphenyl)tris(p-tolyl)porphyrinato]-zinc(II) (3). The zinc(II) porphyrin 3 has large affinity for pyrazole due to the hydrogen bond between pyrazole and the 2-ethoxycarbonyl group in addition to the coordination bonding accompanied by the conformational change of the ethoxycarbonyl group in the coordination process. The (1)H NMR, IR, and UV-vis spectra of 1 and its ESI-MS and VPO measurements have revealed the cyclic trimer structure with an overall association constant of 6.0 x 10(13) M(-2) at 22 degrees C. The contribution of the hydrogen bond to the total free energy change in trimer formation is estimated to be 7.5 kcal/mol based on a reference trimer system without a hydrogen bonding site. The trimer geometry causes characteristic exitonic interaction between porphyrin units to yield a broad Soret band which is deconvoluted into four components by UV-vis and MCD spectral analyses. Electrochemical measurements have shown that only the first ring-oxidation process proceeds stepwise in the trimer.
Ikeda
C
C
Department of Applied Chemistry, and Department of Chemistry, Keio University, 3-14-1 Hiyoshi Kohoku-ku, Yokohama 223-8522, Japan. chusaku@hotmail.com
Tanaka
Y
Y
Fujihara
T
T
Ishii
Y
Y
Ushiyama
T
T
Yamamoto
K
K
Yoshioka
N
N
Inoue
H
H
D004563:Electrochemistry; D006860:Hydrogen Bonding; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008665:Metalloporphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D011487:Protein Conformation; D011720:Pyrazoles / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet
C432008:(5-(pyrazol-4-yl)-10,20-bis(p-tolyl)-15-(2-ethoxycarbonylphenyl)porphyrinato)-zinc(II); D007202:Indicators and Reagents; D008665:Metalloporphyrins; D011720:Pyrazoles