Infinite Three-Dimensional Polymeric Metalloporphyrin Network via Six-Coordinate Zn(II) and Two Axial Oxygen Donors

Abstract

[structure: see text]. An X-ray crystallographic study of zinc(II) 5,15-di-(2-methoxymethylphenyl)-porphyrin indicates that it forms a coordination polymer through ligation of the ether oxygen atoms on the porphyrin peripheries to the metal centers of two identical adjacent porphyrins. This gives a novel extensively linked, three-dimensional polymeric structure in which the zinc(II) metal forms a six-coordination center. The uniquely structured network has cavities between 4.81 and 9.27 angstroms, which makes it resemble molecular sieve materials.

One‐Dimensional, Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

“…[72] Compounds 1Zn-4Zn presented herein all contain eight Lewis basic sites and, in principle, one Lewis acidic site (the zinc atom). [72] Compounds 1Zn-4Zn presented herein all contain eight Lewis basic sites and, in principle, one Lewis acidic site (the zinc atom).…”

“…The ZnÀO distances in bisA C H T U N G T R E N N U N G (THF) complexes of ZnTPP derivatives are between 2.371 [63] and 2.56 , [68] and in a zinc(II) porphyrin polymer the Zn À O benzylmethylether distances were found to be 2.434 . [72] In the case of [3Zn] 1 , the phenyl groups connected to the coordinating EBrE donor groups (E = OMe) are bent out of the porphyrin plane by 13.7(8)8 away from the adjacent zinc(II) porphyrin unit; this arrangement pulls two adjacent porphyrin rings closer together. The noncoordinating EBrE groups again adopt a normal geometry.…”

Chiral recognition of cyclic α‐hydroxyketones by CD‐sensitive zinc tetraphenylporphyrin tweezer

“…38,43 Thus the (3-hydroxypropylamino)acetyl group HOCH 2 CH 2 CH 2 NHCH 2 CO-was tested as a new carrier moiety to produce ''hydroxyconjugate'' 2b (Scheme 4). First, we applied method C, where 3-aminopropane is used instead of diaminopropane (see method A).…”

“…Molecular modeling calculations were performed as described earlier 33,34,36,37 with the following modification: (i) sampling of all the structures was adopted within 15 kJ/ mol instead of 10 kJ/mol of the lowest-energy conformer over 1,000 fully optimized steps, (ii) the distance checks for primary alcohol O -Zn were set to 2.4 F 0.5 Å , 38 and (iii) the dihedral angles around the stereogenic center [Ha -Ca -O -C(=O) dihedral] of the guest, a-hydroxyketone derivatives, were locked in order to find the lowestenergy conformations within a limited calculation time. 39,40 After all the calculations (3,000 times), the most stable conformers within a 15-kJ/mol energy window were analyzed using the Boltzmann distribution based on energy difference.…”

62 Porphyrin-Based Tectons in Molecular Tectonics

“…Another 3D arrangement has been reported for zinc(II) 5,15-di-(2-methoxymethylphenyl)porphyrin. 73 The self-complementary tecton crystallizes in the tetragonal space group (I4 1 /a) ( Figure 14). …”