π‐Extended “Earring” Porphyrins with Multiple Cavities and Near‐Infrared Absorption

Abstract

β,β-tripyrrin-bridged earring porphyrins were synthesized through Suzuki-Miyaura cross coupling reactions. These porphyrinoids have multiple cavities and can accommodate two or three metal ions per molecule. The structures of the porphyrins have been elucidated by x-ray diffraction analysis, and feature curved π planes. The electronic spectra of the porphyrins exhibit near-infrared (NIR) absorptions and metal insertion leads to red-shifted and intensified absorption features. Electrochemical analysis and transient absorption measurements indicated that the porphyrins exhibit effective electronic communication between their central and peripheral moieties.

A Perspective on the Trends and Challenges Facing Porphyrin‐Based Anti‐Microbial Materials

“…Song and co‐workers. The new structure features of these π‐extended porphyrins and exhibited near‐infrared absorption provide them the opportunity to be potential PSs in future . Meanwhile, the combination of the porphyrin molecules across the field of nanotechnology, antibodies coupling, magnetic recoverable systems and bioimaging are expected to yield a flourishing of applications at the frontier of multidisciplinary PDI.…”

Synthesis, Structures, and Near‐IR Absorption of Heterole‐Fused Earring Porphyrins

“…report) [3] has been now improved up to 68 %b yo ptimizing the synthetic conditions.I mportantly,w ef ound that regioselective bromination of 1 with NBS proceeded smoothly at 0 8 8C in CHCl 3 to give 2 in 64 %y ield. Synthesis of earring porphyrins fused with thiophener ings.…”

π‐Extended “Earring” Porphyrins with Multiple Cavities and Near‐Infrared Absorption

“…Both the C-N distance 4.505(3) a nd the N-N distance 4.064(4) o ft he newly formed cavity are longer than the N-N distance (ca. 3.84 ) of porphyrin, so the new cavity is bigger than the porphyrin central cavity.T he dihedral angle between the "face" and the "ear" is 162.12(4)8 8,a nd the N-C-Ni angle is 175.33(9)8 8.The CÀCdistance between "face" and the "ear" is 1.450(3) f or 4a,1.409 (7) f or 4a-Pd. [8] In 4a-Pd,P d II insertion resulted in an increase of the maximum displacement of the porphyrin plane to 0.759(4) , ad ecrease in the dihedral angle between the "face" and the "ear" to 150.5677(4)8 8,and adecrease in the N-C-Ni angle to 166.5687(4)8 8,t hus inducing further curvature of the earring porphyrin.…”

“…[5] b,b'-dibromo Ni II porphyrin 2a was synthesized as previously reported. [7] Compound 4a has as moothly curved plane and the maximum displacement of the porphyrin plane is Scheme 1. After oxidation and purification, 4a was obtained in 30 %y ield.…”

“…[8] Thef inal structural confirmation of 4a and 4a-Pd were obtained from single-crystal X-ray diffraction analysis (Figure 1b,d). [7] Compound 4a has as moothly curved plane and the maximum displacement of the porphyrin plane is Scheme 1. Structures of porphyrins, earring porphyrins,and their metal complexes.…”