Synthesis, structures and properties of benzoporphycenes and naphthoporphycenes

A series of benzoporphycenes and naphthoporphycenes and their zinc complexes were prepared from bicyclo[2.2.2]octadiene fused porphycenes by a retro-Diels-Alder reaction and their photophysical properties were studied. Free-base tetranaphthoporphycene was not soluble in common organic solvents, but zinc tetranaphthoporphycene was slightly soluble in pyridine and showed B- and Q-bands at 507 and 690 nm, respectively. Dinaphthoporphycene showed broad B- and Q-bands due to its lower symmetry. Tetrabenzo-, dibenzo-, and dinaphthoporphycenes showed fluorescence at 673, 654, and 670 nm with quantum yields of 0.32, 0.42, and 0.31, respectively, although their precursors were non-fluorescent. Zinc complexes of tetrabenzo-, dibenzo-, tetranaphtho-, dinaphthoporphycenes and their bicyclo[2.2.2]octadiene-fused precursors revealed moderate fluorescence with quantum yields of 0.15–0.37. The crystal structures of tetrabenzo- and dibenzoporphycenes showed herringbone structures, while the zinc tetrabenzoporphycene showed a hexagonal box-structure with six pyridine ligands inside.

[1]  E. Vogel,et al.  Steric Modulation of the Porphycene System by Alkyl Substituents: 9,10,19,20‐Tetraalkylporphycenes , 1989 .

[2]  Johann Lex,et al.  Porphycene—a Novel Porphin Isomer , 1986 .

[3]  K. Houk,et al.  PALLADIUM COMPLEXES OF THE NEW PORPHYRIN ISOMERS (Z)- AND (E)-ISOPORPHYCENE : PDII-INDUCED CYCLIZATION OF TETRAPYRROLEALDEHYDES , 1997 .

[4]  J. Sessler,et al.  Porphycenes: synthesis and derivatives. , 2008, Chemical Society reviews.

[5]  H. Yamada,et al.  Synthesis, structures, and optical and electrochemical properties of benzoporphycenes. , 2009, Chemistry.

[6]  A. Phadke,et al.  A new porphycene‐derived ring structure: octaethylbenzochloracene , 2001 .

[7]  E. Vogel,et al.  2,7,12,17‐Tetrapropylporphycene—Counterpart of Octaethylporphyrin in the Porphycene Series , 1987 .

[8]  H. Yamada,et al.  Synthesis and characterization of tetraanthroporphyrins. , 2008, Organic letters.

[9]  H. Yamada,et al.  First synthesis of dodecasubstituted porphycenes. , 2011, Chemistry.

[10]  G. Sheldrick.  A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[11]  E. Vogel,et al.  New Porphycene Ligands: Octaethyl‐ and Etioporphycene (OEPc and EtioPc)—Tetra‐ and Pentacoordinated Zinc Complexes of OEPc , 1993 .

[12]  J. Sessler,et al.  CORRPHYCENE : A NEW PORPHYRIN ISOMER , 1994 .

[13]  Yoshiharu Sato,et al.  Columnar structure in bulk heterojunction in solution-processable three-layered p-i-n organic photovoltaic devices using tetrabenzoporphyrin precursor and silylmethyl[60]fullerene. , 2009, Journal of the American Chemical Society.

[14]  Lisa R. Pattison,et al.  Solution-processed nickel tetrabenzoporphyrin thin-film transistors , 2006 .

[15]  J. Sessler,et al.  Expanded, Contracted & Isomeric Porphyrins , 1997 .

[16]  H. Yamada,et al.  SYNTHESIS OF TETRABENZOPORPHYRINS FUSED WITH FLUORANTHENES , 2010 .

[17]  Maria Cristina Burla,et al.  SIR97: a new tool for crystal structure determination and refinement , 1999 .

[18]  J. Sessler,et al.  Octaethylhemiporphycene: Synthesis, Molecular Structure and Photophysics†‡ , 1997 .

[19]  E. Vogel.  The porphyrins from the 'annulene chemist's' perspective , 1993 .