BIS[(TETRAPHENYLPORPHYRINATO)ZINC]–CALIX[4]PYRROLE.
565
β-H), 7.33 d (8H, o-H), 7.76 m (11H, m-H, p-H),
1.40 s (3H, CH3), 2.81 s (2H, NH). Mass spectrum:
m/z 657.5 [M]+.
(XXXII). Compound XXXI, 5 mg, was dissolved in
70 mL of dimethylformamide, excess (10 equiv) of
zinc acetate was added, and the mixture was heated for
30 min under reflux. The mixture was cooled and
diluted with an equal volume of water, and the precip-
itate was filtered off, dried, and subjected to chroma-
tography on aluminum oxide using methylene chlo-
ride–hexane (1:2) as eluent. The eluate was evaporated
under reduced pressure, and the residue was recrystal-
lized from methylene chloride–methanol (1:1). Yield
4.5 mg (90%), Rf 0.45 (Al2O3, CH2Cl2–hexane, 1:2).
Electronic absorption spectrum (toluene), λmax, nm
5-[4-(5-Methyldipyrrometan-5-yl)phenyl]-
10,15,20-triphenylporphyrin (XXX). A solution of
5.26 mL of (0.075 mmol) of pyrrole in 50 mL of
ethanol was added dropwise under stirring to a solution
of 9.66 mg (0.015 mmol) of compound XXVI in
100 mL of ethanol–methylene chloride (5:1 by
volume). The mixture was heated to the boiling point,
2 mL of aqueous HCl was added, and the mixture was
heated for 30 min under reflux, cooled, and diluted
with 150 mL of water. The organic phase was separat-
ed and washed with water, and the solvent was
removed under reduced pressure. The residue was sub-
jected to chromatography on aluminum oxide using
methylene chloride–hexane (1:1) as eluent. The eluate
was evaporated under reduced pressure, and the oily
residue was brought into the next step without ad-
ditional purification. Electronic absorption spectrum
(toluene), λmax, nm (logε): 647 (3.62), 591 (3.96), 549
1
(logε): 588 (3.87), 548 (4.08), 416 (4.81). H NMR
spectrum, δ, ppm: 8.66 br.s (8H, β-H), 8.59 br.s (8H,
β-H), 7.30 d (16H, o-H), 7.72 m (22H, m-H, p-H),
7.23 br.s (4H, NH, calixpyrrole), 5.70 d (8H, β-H,
calixpyrrole), 0.41 s (12H, CH3), –0.37 s (6H, CH3).
Mass spectrum: m/z 1756.9 [M]+.
The stability constants of the bis[porphyrinato-
(zinc)] complexes with 1,4-diazabicyclo[2.2.2]octane
(L) were determined by spectrophotometric titration
using the following equation [25]:
1
(4.27), 515 (4.53), 418 (5.01). H NMR spectrum, δ,
ppm: 8.72 br.s (8H, β-H), 7.36 d (8H, o-H), 7.79 m
(11H, m-H, p-H), 7.21 br.s (2H, NH, pyrrole), 6.18 s
(2H, α-H, pyrrole), 5.70 d (4H, β-H, pyrrole), 1.44 s
(3H, CH3), 2.83 s (2H, NH, porphyrin).
[A·B]
1
ΔAi, λ1 ΔA0, λ2
Ks =
=
(L/mol).
[A] [B] [B] ΔA0, λ1 ΔAi, λ2
2,2,4,6,6,8-Hexamethyl-4,8-bis[4-(10,15,20-tri-
phenylporphyrin-5-yl)phenyl]-1,3,5,7(2,5)-tetra-
pyrrolacyclooctaphane (XXXI). Trifluoroacetic acid,
1 mL, was added under stirring to a mixture of 10 mg
of compound XXX and 50 mL of acetone, and the
mixture was stirred for 30 min at room temperature.
The mixture was then treated in succession with 20 mL
of 10% aqueous K2CO3 and 50 mL of methylene chlo-
ride, and the organic phase was separated, washed with
water, dried over Na2SO4, and subjected to chromatog-
raphy on aluminum oxide using methylene chloride–
hexane (1:2) as eluent. Yield 5.7 mg (48%), Rf 0.53
(Al2O3, CH2Cl2–hexane, 1:2). Electronic absorption
spectrum (toluene), λmax, nm (logε): 644 (3.31), 590
Here, λ1 is a descending wavelength, λ2 is an as-
cending wavelength, [A] is the concentration of bis-
[(porphyrinato)zinc]–calix[4]pyrrole, [B] is the ligand
concentration, ∆A0 is the maximum variation of the
optical density at a given wavelength, and ∆Ai is the
variation of the optical density at a given wavelength
at a given concentration.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 12-03-00775, 14-03-00011, 14-03-00009), by the
Chemistry and Materials Science Department of the
Russian Academy of Sciences (program no. 6, “Chem-
istry and Physical Chemistry of Supramolecular
Systems and Atom Clusters”), and by the Presidium of
the Russian Academy of Sciences (program no. 24,
“Nanodrugs and Their Targeted Delivery”) with the
use of the facilities provided by the center for joint use
of scientific equipment “The Upper Volga Region
Center of Physicochemical Research.”
1
(3.87), 548 (4.08), 513 (4.33), 414 (4.81). H NMR
spectrum, δ, ppm: 8.67 br.s and 8.60 br.s (8H each,
β-H), 7.31 d (16H, o-H), 7.74 m (22H, m-H, p-H),
7.24 br.s (4H, NH, calixpyrrole), 5.72 d (8H, β-H,
calixpyrrole.), 0.42 s (12H, CH3), –0.39 s (6H, CH3),
2.89 br.s (4H, NH, porphyrin). Mass spectrum:
m/z 1625.3 [M]+.
REFERENCES
5,5′-[2,4,4,6,8,8-Hexamethyl-1,3,5,7(2,5)-tetra-
pyrrolacyclooctaphane-2,6-diylbis(benzene-4,1-di-
yl)]bis[(10,15,20-triphenylporphyrinato)zinc]
1. Gale, P.A., Sessler, J.L., and Kràl, V., Chem. Commun.,
1998, p. 1.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 4 2014
Mamardashvili
