Star porphyrazines: peripheral chelation of porphyrazineoctathiolate by diphosphinonickel ions

Abstract

We have synthesized new pentametallic macrocyclic complexes based on the polynucleating ligand, porphyrazine- 2,3,7,8,12,13,17,18-octathiolate, (pzot)8-. This ligand can be thought of as a porphyrazine (tetraazaporphyrin) bearing four dithiolene moieties peripherally at the /3-pyrrole positions, and we show that a transition-metal ion can be chelated to each of the four peripheral dithiolene moieties. The complexes [(P-P)Ni]4[Ni(pzot)] (2a, P-P = dppe; 2b, P-P = dppy; 2c, P-P = dppb; 2d, P-P = dope) have been synthesized and characterized. Complex 2a crystallizes in the orthorhombic space group Cmc2i (No. 36) with 4 macrocycles and 16 solvent molecules (Ñ,/V-dimethylformamide) in a unit cell of dimensions a = 24.630(5) Á, b = 20.607(4) Á, c = 30.675(6) Á. The [Ni(pzot)]8ligand in 2a coordinates four Ni(P-P) moieties around its periphery with the two thiolate sulfur atoms of each pyrrole binding a nickel ion in a bidentate (S-S) coordination mode. This is in contrast to the reaction of [Ni(pzot)]8-with SnR^Xi, which yielded Ni(pzot)(SnR.2)4 (1), where each tin is coordinated in the tridentate (S-N-S) mode, with the thiolate sulfur atoms from two pyrroles and one w-nitrogen atom as ligands from the macrocycle (Velázquez, C. S.; Fox, G.

Redox-Active Metallodithiolene Groups Separated by Insulating Tetraphosphinobenzene Spacers

“…These fold angles, φ, are shown in Tables 2 and 3 for all compounds. Because the tpbz fold angle does not disrupt planarity in the 89.98 [3] 91.22 [1] 93.009 [1] 91.53 [2] 91.80 [1] 92.751 [12] 88.33 [2] 87.99 [1] 88.023 [11] 89.33[1] X−M−P trans b,c 173.69 [3] 176.42 [1] 175.630 [11] 165.55 [2] 164.72 [1] 176.853 [12] 173.18 [2] 172.28 [2] 176.590 [13] 175.25 [ 85.82 [4] 87.30 [2] 89.17 [3] 89.57(2) 85.23 [3] 84.52( 14) SMP cis 90.40 [8] 90.50 [1] 92.44 (7) 92.57 [3] 90.19 [2] 92.73 [3] 91.99 [3] 91.93 [2] 91.78 [1] 93.34 [2] m 96.81( 14) SMP trans 167.35 [8] 173.37 [2] 178.87 (9) 175.64 [2] 177.37 [3] 175.16 [3] 176.21 [3] 163.54 [3] 163.47 [2] 173.41 [2] immediate environment of the metal atom, it occurs with a magnitude and frequency unrelated to the identity of the metal atom. The consequence of twisting of t...…”

“…The following procedure is a modification of a published preparation. 9 A mixture of [NiCl 2 (dppb)] (0.100 g, 0.17 mmol) and [(mnt)SnMe 2 ] (0.75 g, 2.6 mmol) was dissolved in dichloroethane (30 mL) and refluxed with stirring for 2 h. The resulting reddish-brown colored solution was then cooled to ambient temperature, and the solvent was removed under reduced pressure. The residual solid was washed with MeOH (2 × 3 mL) followed by Et 2 O (2 × 5 mL) and then dried under vacuum.…”

“…Figure illustrates a representative variety of multimetal complexes in which both dithiolene ligands and other “functional elements” are incorporated. − The other functional elements may be structural components only, other redox-active centers, chromophores separate from or conjugated to the metallodithiolene moiety, or some combination of the foregoing. In an earlier report , intended as a prelude to a well-defined set of metallodithiolene oligomers, we described the synthesis and properties of di- and trimetallic 1,2,4,5-tetrathiolatobenzene-linked complexes of the group 10 metals which employed chelating diphosphines as stable, capping end-groups (Figure a).…”

Synthesis, spectroscopy and electrochemistry of phthalocyanine derivatives functionalised with four and eight peripheral tetrathiafulvalene units

“…1 There is keen current interest in exploring new structural modifications to the phthalocyanine system, including the study of binuclear derivatives, 2 heterocyclic analogues 3 in which the benzene rings are replaced by nitrogen-containing 3a-d or sulfur-containing 3e,f heterocycles, and derivatives with specially-designed 'active' peripheral substituents, viz. thiolate groups which coordinate transition metals, 4 a fullerene moiety which undergoes electrochemical reduction, 5 flexible unsymmetrical substituents which result in glasses, 6 mesogenic metal-chelated crown ethers which form nanometre-sized molecular cables, 7 glycol side-chains to hinder aggregation and thereby increase the luminescence quantum yield 8 and liquid crystalline ferrocenyl-and tetrathiafulvalenyl-phthalocyanine derivatives. 9 In a recent communication we reported the synthesis of compound 1 bearing eight tetrathiafulvalene (TTF) substituents which provided the first example of the covalent attachment of phthalocyanine (Pc) and TTF units.…”

Crystal Structure of [Bis(1,2-diphenylphosphino)ethane](maleonitriledithiolato)-nickel(II) [Ni(dppe)(mnt)]·CH2Cl2

“…3 We succeeded in obtaining a single crystal (redbrown cubic) suitable for X-ray structural analysis from the recrystallization of a sample prepared by the method of Cambell et al2 in a mixture of CH2C12 and hexane. Here, the structure of the CH2C12 solvate of [Ni(dppe)- The crystal data and experimental conditions are given in Table 1.…”