title: Synthesis and properties of fused-ring-expanded porphyrins that were core-modified with Group 16 heteroatoms.
abstract: The synthesis of a series of novel core-modified and fused-ring-expanded tetraphenylporphyrins is reported. Theoretical calculations and magnetic circular dichroism (MCD) and fluorescence spectroscopic measurements were used to analyze the effect of core modification with Group 16 oxygen, sulfur, selenium, and tellurium atoms on the optical properties and electronic structures of the porphyrins. Marked redshifts of the Q and B bands and accelerated intersystem-crossing rates were observed, thus making these compounds potentially suitable for use in a variety of applications. The scope for further fine-tuning of these optical properties based on additional structural modifications, such as the incorporation of fused benzene rings to form ABAB structures by using a thiophene precursor with a fused bicyclo[2.2.2]octadiene ring and the introduction of various substituents onto the meso-phenyl rings, is also examined.
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, PR China.
authors.forename: Hai-Jun
authors.initials: HJ
authors.lastname: Xu
authors.forename: John
authors.initials: J
authors.lastname: Mack
authors.forename: Di
authors.initials: D
authors.lastname: Wu
authors.forename: Zhao-Li
authors.initials: ZL
authors.lastname: Xue
authors.forename: Ana B
authors.initials: AB
authors.lastname: Descalzo
authors.forename: Knut
authors.initials: K
authors.lastname: Rurack
authors.forename: Nagao
authors.initials: N
authors.lastname: Kobayashi
authors.forename: Zhen
authors.initials: Z
authors.lastname: Shen
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000737:chemistry; D002942:Circular Dichroism; D018360:Crystallography, X-Ray; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry*; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D012643:Selenium / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D013455:Sulfur / Q000737:chemistry*; D013691:Tellurium / Q000737:chemistry*; D013876:Thiophenes / Q000737:chemistry
chemical_list: D001643:Bridged Bicyclo Compounds; D011166:Porphyrins; D013876:Thiophenes; C409084:tetraphenylporphyrin; D013455:Sulfur; D012643:Selenium; D013691:Tellurium; D010100:Oxygen