Crystal Structure and Silver Ion Complexation of a Novel Porphyrazine Substituted with four Dithiacrown ether Rings

Abstract

Abstract. The synthesis of magnesium porphyrazines substituted with sulfur-containing 15-crown-5 and 18-crown-6 macrocycles is reported as well as the single crystal structure of the 18-crown-6 substituted porphyrazine; the larger crown ether compound is shown to form dimers with Ag+ ions, unlike the porphyrazine with the smaller crown ether rings. Supramolecular structures from phthalocyanine and porphyrin building blocks are currently receiving great interest.1-6 As part of our program aimed at the development of conducting materials7 from such structures, we describe here the first synthesis and metal ion binding properties of novel porphyrazines l(n) (n= 1,2) substituted at the P-positions with crown-ether rings. In addition, we present the first X-ray structure of a crowned porphyridphthalocyanine type of molecule. The crown ether precursors 2(1) and 2(2) were prepared from sodium cis-1,2-dicyano-1,2-ethylenedithiolate8 and tetraethyleneglycol-dichloride (1 1 % yield) and pentaethyleneglycol-dichloride (23% yield), respectively, according to a slightly modified literature pro~edure.~ To a boiling suspension of 5 mmol magnesium in 10 mL npropanol was added a solution of 1 mmol of 2(n) in 10 mL n-propanol and the reaction mixture was refluxed for 18 h. The product was isolated and purified by washing with acetone and dry diethylether and subsequently by column chromatography (NaBr impregnated silica, eluent 2% MeOH in CHC13 for 1(1), and 10% MeOH in CHC13 for l(2)). Compounds l(1) and l(2) were obtained as dark blue fb3 e, ,s powders in yields of 22% and 20%, respectively (1n.p. > 320 "C).t Single crystals of l(2) were grown from CHC13/MeOH (1:l). X-ray data were collected on an Enraf-Nonius Cad4-Ttrotating anode diffractometer [MoKa (Mon); 150 K1. The compound crystallized in a triclinic unit cell, spaceroup P1, a = 9.584(3) 8, b = 17.672(2) A, c = 19.620 (4) x, ~1 = 84.904(14)", p = 85.21(2)", y = 89.29(2)", V = 3298.3(13) A3, Z = 2. The structure was solved with SIR92 and refined using SHELXL92, resulting in R1 = 0.093, wR2 = 0.252, and S = 0.983. A PLUTON-plot is presented in Figure 1. The magnesium atom in the center of the porphyrazine is coordinated by one water molecule (probably from the solvent), which is linked with two bifurcated H-bonds to the crown ether ring of a neighboring porphyrazine. In this way a linear staircase-like structure is obtained. The nearest distance between the centers of two porphyrazine molecules amounts to 9.584(5) 8. A detailed description of the structure will be published elsewhere.1° The binding affinities of compounds l ( n ) for silver(1) perchlorate were evaluated by UV/vis spectroscopy. On addition of an AgC104 solution to a solution of the 18-crown-6 derivative l(2) in 5% MeOH in CHC13, the t The products were fully characterized by elemental analysis and spectroscopic techniques. Compound 1 (1): UV/vis (CHC13) kmax/nm(log E): 675

Synthesis, characterization and computational investigation of novel metalloporphyrazines containing 15-membered O2S2-donor macrocyclic moieties

“…The first synthesis of crownfused porphyrazines has been accomplished by the groups of Hoffman and Nolte [8][9][10]. Porphyrazine derivatives, which contain soft sulfur donor atoms, play an important role in affecting the solidstate interactions, and the sulfur atoms in the macrocyclic unit also give the opportunity to bind soft transition metal cations [11][12][13]. In addition, the electronwithdrawing effect of the maleonitrile moiety may reduce the electron-donating ability of sulfur donors in macrocyclic units, and this kind of heteroatoms strongly perturb the porphyrazine grand state transition and shifting to visibletonearIR region [14].…”

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ABSTRACT: New metalloporphyrazines (MgPz, ZnPz) containing peripheral tetrasubstitutions derived from 7,8dihydro6H,14H,19Hdibenzo[bj] [1,12,5,8]dioxadithiacyclopentadecine16,17dicarbonitrile (6) have been synthesized by a multistep reaction sequence and characterized. Compound 6 has been prepared by the reaction of 1,3di(2bromomethyl phenoxy) propane (3) or 1,3di(2iodomethylphenoxy) propane (4) which were prepared via bromination or iodination of {2[3(2hydroxymethylphenoxy) propoxy]phenyl} methanol (2) and cis1,2dicyano1,2ethylenedithiolate (5).

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Synthesis and electron donating property of novel porphyrazines containing tetrathiacrown ether-linked tetrathiafulvalene moieties

“…In contrast to the crowned Pcs systems, dithiacrowned Pz offers an advantage over its Pc counterparts in that two donor atoms in each crown are in direct conjugation with the 18 p-electron core of the macrocycle. Indeed, these crowned Pzs showed a profound effect on the optical properties of the Pz core, and the sulfur atoms in the crown ether rings give the opportunity to bind soft transition-metal ions [20][21][22][23][24].Very recently, Nolte and co-workers [25] and Liu and coworkers [26] independently reported the preparation of novel tetra(TTF-crown-ether) Pcs and tetra (dithiacrown ether-TTF) Pcs, respectively. It is noteworthy that a tetra (TTF-dithiacrown ether) Pc was found to self-assemble into helical tapes (nanometers in width and micrometers in length) and showed potentially novel electronic and structural properties.…”

Synthesis and characterization of novel supercryptands-fused porphyrazines

“…With the inherent synthetic ease of including diverse peripheral substituents, they are seen as promising materials having potential applications in diverse areas [2]. The first synthesis of crowns-fused porphyrazines was reported independently by the groups of Hoffman and Nolte [3,4]. The coordination chemistry, aggregation and electrical properties of these compounds were investigated [5,6].…”

“…The coordination chemistry, aggregation and electrical properties of these compounds were investigated [5,6]. Such systems contain a metal center that is complexed by a porphyrazine ring, four macrocyclic binding and tridentate meso-pocket sites [3][4][5][6]. That is why such compounds, which are exemplified by [(S 2 ,O 3 crown] 4 pz, should show rich and varied coordination chemistry.…”