title: Synthesis and photophysical properties of doubly β-to-β bridged cyclic Zn(II) porphyrin arrays.
abstract: A series of doubly β-to-β bridged cyclic Zn(II) porphyrin arrays were prepared by a stepwise Suzuki-Miyaura coupling reaction of borylated Zn(II) porphyrin with different bridge groups. The coupling of the building block of β,β'-diboryl Zn(II) porphyrin 1 with different bridges provided the doubly β-to-β carbazole-bridged Zn(II) porphyrin array 3, the fluorene-bridged Zn(II) porphyrin array 5, the fluorenone-bridged Zn(II) porphyrin array 7, and the three-carbazole-bridged Zn(II) porphyrin ring 8. The structural assignment of 3 was confirmed by the X-ray diffraction analysis, which revealed a highly symmetrical and remarkably bent syn-form structure. The incorporation of bridge units with different electronic effects results in different photophysical properties of the cyclic Zn(II) porphyrin arrays. Comprehensive photophysical studies demonstrate that the electron-withdrawing bridge fluorenone has the largest electronic interaction with the Zn(II) porphyrin unit among the series, thus resulting in the highest two-photon absorption cross-section values (σ((2))) of 6570±60 GM for 7. The present work provides a new strategy for developing porphyrin-based optical materials.
authors: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, P R China.
authors: Qingshan
authors: Q
authors: Hao
authors: Yi
authors: Y
authors: Zeng
authors: Tianjun
authors: T
authors: Yu
authors: Jinping
authors: J
authors: Chen
authors: Guoqiang
authors: G
authors: Yang
authors: Yi
authors: Y
authors: Li
mesh_terms: D018360:Crystallography, X-Ray; D008665:Metalloporphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D055668:Photochemical Processes; D015032:Zinc / Q000737:chemistry*
chemical_list: D008665:Metalloporphyrins; D015032:Zinc