(5,10,15,20-Tetraphenylporphyrinato-κ⁴N)zinc–18-crown-6 (1/1)

Abstract

Key indicators: single-crystal X-ray study; T = 180 K; mean (C-C) = 0.003 Å; disorder in main residue; R factor = 0.039; wR factor = 0.108; data-to-parameter ratio = 14.5.In the title compound, [Zn(C 44 H 28 N 4 )]ÁC 12 H 24 O 6 , the Zn II ion lies on an inversion center and the asymmetric unit contains one half of a Zn(TPP) complex (TPP = 5,10,15,20-tetraphenylporphyrin dianion) and one half of a centrosymmetric 18-crown-6 molecule. The Zn(TPP) complex exhibits a nearly planar conformation of the porphyrin core [maximum deviation = 0.106 (2) Å ] with an average Zn-N distance of 2.047 (2) Å . The title compound is considered as a onedimensional polymer along [010], in which the Zn(TPP) moiety is linked to the closest O atoms of two symmetryrelated 18-crown-6 molecules with a Zn-O distance of 2.582 (1) Å , completing a distorted octahedral coordination environment of the metal ion. The chains are mainly sustained by weak C-HÁ Á Á interactions. An ethylene group of the 18-crown-6 molecule is disordered over three sites with occupancies of 0.50, 0.25 and 0.25. Table 1 Hydrogen-bond geometry (Å , ). Related literatureCg1, Cg2 and Cg3 are the centroids of the N1/C1-C4, N2/C6-C9 and C11-C16 rings, respectively. metal-organic compounds m444 Denden et al.

Exploring the Effects of Axial Pseudohalide Ligands on the Photophysical and Cyclic Voltammetry Properties and Molecular Structures of MgII Tetraphenyl/porphyrin Complexes

“…Several metalloporphyrins containing anionic ligands such as CO 3 2– and N 3 – were prepared by using this synthetic technique 9,10. We noticed that the use of 18‐crown‐6 could result in its coordination to the metal center of the metalloporphyrin as in {[Zn(TPP)(18‐C‐6)]} n 11. Accordingly, we chose to use crypt‐222 rather than the crown ether.…”

Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of ZnII Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands

“…The reported syntheses of zinc porphyrin complexes bearing anionic axial ligands make use of either a mixture of organic‐soluble metal porphyrins and water‐soluble inorganic salts (sources of the anionic ligands), which are effectively incompatible reactants, or the crown ether 18‐crown‐6 (18‐C‐6) to solubilize the salts in organic solvents. To prepare 1 – 4 , we used cryptand‐222 instead of the much cheaper 18‐C‐6, which can coordinate to the zinc center as in the {[Zn(TPP)(18‐C‐6)]} n species 15. The reactions of the ( meso ‐tetraphenylporphyrinato)zinc(II) starting material [Zn(TPP)] with an excess of MX salt (M = Na or K; X = azide, cyanate, thiocyanate, or cyanide) in the presence of cryptand‐222 in dichloromethane (CH 2 Cl 2 ) led to the formation of the four target pseudohalide zinc porphyrins: sodium(cryptand‐222) azido( meso ‐tetraphenylporphyrinato)zinc(II) ( 1 ), sodium(cryptand‐222) (cyanato‐ N )( meso ‐tetraphenylporphyrinato)zinc(II) ( 2 ), potassium(cryptand‐222)(thiocyanato‐ N )( meso ‐tetraphenylporphyrinato)zinc(II) ( 3 ), and potassium(cryptand‐222) (cyanido)( meso ‐tetraphenylporphyrinato)zinc(II) ( 4 ).…”