Open Network Architectures from the Self‐Assembly of AgNO₃ and 5,10,15,20‐Tetra(4‐pyridyl)porphyrin (H₂tpyp) Building Blocks: The Exceptional Self‐Penetrating Topology of the 3D Network of [Ag₈(Zn^IItpyp)₇(H₂O)₂](NO₃)₈

Abstract

The use of suitable predetermined building blocks has assumed an increasing relevance in recent times in the crystal engineering of coordination frameworks [1] that have potential interest as zeolite-like materials. [2] In this regard, much d) N. ] Racemic 1 was prepared by the lithiation of 2-alkynyl-5bromopyrimidine followed by treatment with 2-methylpropanal.[8] Preparation of (S)-1 with ca. 0.00005 % ee. Pyrimidyl alkanol (S)-1 (1.5 mg, > 99.5 % ee) was dissolved in ethyl acetate (or benzene) to make a standardized solution of (S)-1 (3.2 î 10 À6 mol L À1 ). The solution (50 mL) was added to a solution of racemic 1 (75.1 mg) in ethyl acetate (or benzene). Then, a part of the solution was transferred to another flask, and the removal of solvent gave (S)-1 with ca. 0.00005 % ee (9.9 mg). Dissolution of the whole (S)-1 in 4.3 mL of cumene produced a 9.9 î 10 À3 m solution of (S)-1 with ca. 0.00005 % ee. [9] a) K. Soai, S. Niwa, Chem. Rev. 1992, 92, 833 ± 856; b) L. Pu, H.-B. Yu, Chem. Rev. 2001, 101, 757 ± 824. [10] After our experiments were completed, Singleton and Vo reported asymmetric autocatalysis using (R)-(2-methylpyrimidyl)alkanol [5b] with the order of 10 À5 % ee [a) D. A. Singleton, L. K. Vo, J. Am. Chem. Soc. 2002, 124, 10 010 ± 10 011]. However, they used only the catalyst with the R configuration. We believe that it is essentially important to examine the asymmetric autocatalysts of both configurations. The reasons are as follows:1) The chirality level of the catalyst on the order of 10 À5 % ee is Sato,

1D and 2D solid-state metallosupramolecular arrays of freebase 5,10,15,20-tetra(4-pyridyl)porphyrin, peripherally linked by zinc and manganese ions

“…In particular, the construction of infinite metallosupramolecular multiporphyrin arrays using the exocyclic coordination ability of the peripheral pyridyl groups of the readily accessible 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP) to external metal ions originated from the pioneering work of Robson and coworkers [5,6]. Up to now many coordination polymers bearing the TPyP moiety as a ligand are known [7][8][9][10][11][12][13][14][15][16][17]. Recently the first discrete metallosupramolecular open molecular box containing TPyP as walls was reported [18].…”

Classification of Structural Motifs in Porphyrinic Coordination Polymers Assembled from Porphyrin Building Units, 5,10,15,20-Tetrapyridylporphyrin and Its Derivatives

“…The 2D sheet-II pattern of 13 (Fig. 9a) is a variation of the previously discussed 1D rod, with a greater stoichiometric ratio of silver atoms to porphyrin units: 2:1 versus 1:1 for the 1D rod [17,26]. A metallated version of this 2D sheet-II 14 (see Fig.…”

“…3). In 4, only two pyridyl arms of each H 2 TPyP molecule are coordinated to a silver metal node [26]. The uncoordinated nature of the ''extra'' pyridyl arms is puzzling until the synthesis conditions are examined.…”

“…TCE tetrachloroethane, DMA N,N 0 -dimethylacetamide, Py pyridine porphyrin structures containing silver salts, such as Ag(NO 3 ) [26] and AgPF 6 [27].…”

Structural Diversity in Tetrakis(4-pyridyl)porphyrin Supramolecular Building Blocks

“…When considering the threedimensional net as a whole, it becomes apparent that the manner of linking of the sql nets together results in the three-dimensional net being self-penetrating, this being only the second reported self-penetrating network structure involving TPyP. 114 As a result of the interconnection of nets in the three-dimensional structure, the connectivity of the Ce-based nodes is increased to six, and their topology becomes more complex. The TPyPbased nodes retain the 4 4 .6 2 topology of the sql nets, while that of the Ce-based nodes becomes 4 4 .6 10 .8, resulting in an overall network topology of (4 4 .6 2 ).…”