TY - JOUR
T1 - Structural changes in non-planar octaaryl substituted phthalocyanine phosphorus complexes
AU - Furuyama, Taniyuki
AU - Harako, Ryosuke
AU - Kobayashi, Nagao
N1 - Funding Information:
This work was partly supported by Grant-in-Aids for Scientific Research on Innovative Areas (25109502, “Stimuli-responsive Chemical Species”), Scientific Research (B) (No. 23350095), Challenging Exploratory Research (No. 25620019) and Young Scientist (B) (No. 24750031) from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT). The authors thank Prof. Takeaki Iwamoto and Dr. Shintaro Ishida (Tohoku University) for X-ray measurements. Some of the calculations were performed using supercomputing resources at the Cyberscience Center of Tohoku University.
Publisher Copyright:
© 2015 World Scientific Publishing Company.
PY - 2015/1/1
Y1 - 2015/1/1
N2 - Phosphorus complexes of non-planar α-octaaryl phthalocyanine derivatives ((α-Ar)8Pc), 3a and 3b have been synthesized by introduction of phosphorus(V) ions into free-base Pcs 2a and 2b. 3a and 3b were characterized by MS, 1H and 31P NMR spectra. The solid state structure of 3a indicated a ruffled Pc structure due to the small atomic radius of phosphorus, although the corresponding free-base Pc 2a has a saddled Pc structure. The phosphorus complexes showed intense absorption bands (Q-bands) in the near-IR region, while the introduction of electron-donating groups at the peripheral phenyl groups was efficient for additional red-shifting of the Q-band. Electrochemical data revealed that the red-shift of the Q-band is attributable to a decrease in the HOMO-LUMO gap due to significant and moderate stabilization of the LUMO and HOMO, respectively. MO calculations suggested that the phosphorus(V) ion intensified the electronic interaction between the peripheral aryl moieties and the Pc macrocyclic core.
AB - Phosphorus complexes of non-planar α-octaaryl phthalocyanine derivatives ((α-Ar)8Pc), 3a and 3b have been synthesized by introduction of phosphorus(V) ions into free-base Pcs 2a and 2b. 3a and 3b were characterized by MS, 1H and 31P NMR spectra. The solid state structure of 3a indicated a ruffled Pc structure due to the small atomic radius of phosphorus, although the corresponding free-base Pc 2a has a saddled Pc structure. The phosphorus complexes showed intense absorption bands (Q-bands) in the near-IR region, while the introduction of electron-donating groups at the peripheral phenyl groups was efficient for additional red-shifting of the Q-band. Electrochemical data revealed that the red-shift of the Q-band is attributable to a decrease in the HOMO-LUMO gap due to significant and moderate stabilization of the LUMO and HOMO, respectively. MO calculations suggested that the phosphorus(V) ion intensified the electronic interaction between the peripheral aryl moieties and the Pc macrocyclic core.
KW - electronic structure
KW - near-infrared absorption
KW - phosphorus phthalocyanine
KW - ruffled structure
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U2 - 10.1142/S1088424615500364
DO - 10.1142/S1088424615500364
M3 - Article
AN - SCOPUS:84928559875
SN - 1088-4246
VL - 19
SP - 500
EP - 509
JO - Journal of Porphyrins and Phthalocyanines
JF - Journal of Porphyrins and Phthalocyanines
IS - 1-3
ER -