The syn
thesis of novel magnesium, copper, andmetal-free porphyrazines, peripherally substituted wi
thdi
thia-7-crown-2 (MPz(7)), di
thia-15-crown-5 (MPz(15)), anddi
thia-18-crown-6 (MPz(18)) macrocycles is reported.These compounds are prepared starting from dicyanoe
thylenecontaining crown e
thers
3,
2(1), and
2(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 di
thia-18-crown-6-substituted porphyrazines,
the dimers break up to form monomeric6:1 guest-host complexes when more
than 2 equiv of
the metal ion is added. The single-crystalstructures of
the crown e
ther
2(2) and
theporphyrazineMgPz(18) are presented. CompoundC
14H
20N
2O
4S
2(
2(2)) crystallizes in
the monoclinic space group
P2
1/
c wi
tha = 10.9310(13) Å,
b = 19.383(3)Å,
c = 8.6976(14) Å,
![](/images/gifchars/beta2.gif)
= 108.898(11)
![](/images/entities/deg.gif)
,
V = 1743.5(5) Å
3, and
Z =4. Thestructure refinement converged to
R = 0.0366 and
Rw = 0.0504. CompoundC
56H
82MgN
8O
17S
8(MgPz(18))crystallizes in
the triclinic space group
P![](/images/entities/onemacr.gif)
wi
tha = 9.584(3) Å,
b = 17.672(2) Å,
c = 19.620(4) Å,
![](/images/gifchars/alpha.gif)
= 84.904(14)
![](/images/entities/deg.gif)
,
![](/images/gifchars/beta2.gif)
= 85.21(2)
![](/images/entities/deg.gif)
,
![](/images/gifchars/gamma.gif)
= 89.29(2)
![](/images/entities/deg.gif)
,
V = 3298.4(13) Å
3, and
Z =2. The structure refinement converged to R1= 0.0839 and wR2 = 0.2196. The electrical properties ofH
2Pz(18) have been studied by compleximpedancespectroscopy. The bulk electrical conductivity of
this compound isapproximately 1 order of magnitude higher
than
that of
the corresponding 18-crown-6 ph
thalocyanine.