Dithiacrown Ether Substituted Porphyrazines: Synthesis, Single-Crystal Structure, and Control of Aggregation in Solution by Complexation of Transition-Metal Ions
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- 作者：Cornelus F. van Nostrum ; Franciscus B. G. Benneker ; Hugo Brussaard ; Huub Kooijman ; Nora Veldman ; Anthony L. Spek ; Joop Schoonman ; Martinus C. Feiters ; and Roeland J. M. Nolte
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：February 14, 1996
- 年：1996
- 卷：35
- 期：4
- 页码：959 - 969
- 全文大小：324K
- 年卷期：v.35,no.4(February 14, 1996)
- ISSN：1520-510X
文摘
The synthesis of novel magnesium, copper, andmetal-free porphyrazines, peripherally substituted withdithia-7-crown-2 (MPz(7)), dithia-15-crown-5 (MPz(15)), anddithia-18-crown-6 (MPz(18)) macrocycles is reported.These compounds are prepared starting from dicyanoethylenecontaining crown ethers 3, 2(1), and2(2), respectively,which contain sulfur as well as oxygen heteroatoms. The"crowned" porphyrazines bind silver(I) andmercury(II) perchlorates. UV/vis spectroscopy and electron paramagneticresonance measurements reveal that additionof the transition-metal ions leads to dimerization of the porphyrazinecomplexes. In the case of the dithia-18-crown-6-substituted porphyrazines, the dimers break up to form monomeric6:1 guest-host complexes when morethan 2 equiv of the metal ion is added. The single-crystalstructures of the crown ether 2(2) and theporphyrazineMgPz(18) are presented. CompoundC14H20N2O4S2(2(2)) crystallizes in the monoclinic space groupP21/c witha = 10.9310(13) Å, b = 19.383(3)Å, c = 8.6976(14) Å, 
= 108.898(11)
,V = 1743.5(5) Å3, and Z =4. Thestructure refinement converged to R = 0.0366 andRw = 0.0504. CompoundC56H82MgN8O17S8(MgPz(18))crystallizes in the triclinic space group P
witha = 9.584(3) Å, b = 17.672(2) Å,c = 19.620(4) Å, 
= 84.904(14), = 85.21(2), 
= 89.29(2),V = 3298.4(13) Å3, and Z =2. The structure refinement converged to R1= 0.0839 and wR2 = 0.2196. The electrical properties ofH2Pz(18) have been studied by compleximpedancespectroscopy. The bulk electrical conductivity of this compound isapproximately 1 order of magnitude higherthan that of the corresponding 18-crown-6 phthalocyanine.
= 108.898(11),V = 1743.5(5) Å3, and Z =4. Thestructure refinement converged to R = 0.0366 andRw = 0.0504. CompoundC56H82MgN8O17S8(MgPz(18))crystallizes in the triclinic space group P witha = 9.584(3) Å, b = 17.672(2) Å,c = 19.620(4) Å, = 84.904(14), = 85.21(2), = 89.29(2),V = 3298.4(13) Å3, and Z =2. The structure refinement converged to R1= 0.0839 and wR2 = 0.2196. The electrical properties ofH2Pz(18) have been studied by compleximpedancespectroscopy. The bulk electrical conductivity of this compound isapproximately 1 order of magnitude higherthan that of the corresponding 18-crown-6 phthalocyanine.