The novel pyridine-containin
g 14-membered macrocycle 3,11-dithia-7,17-diazabicyclo[11.3.1]heptadeca-1(17),13,15-triene (
L), which contains an N
2S
2 donor set, was synthesized, and its protonation behavior was studied byabsorption titration with CH
3SO
3H. The reaction of
L with Pd(II) was studied spectroscopically, and the square-planar complex [Pd(
L)](BF
4) was isolated and characterized. The reactions between
L and NiX
2·6H
2O (X = BF
4,ClO
4) in ethanol or acetonitrile afforded the octahedral complexes [Ni(CH
3CN)(H
2O)(
L)](X)
2 and [Ni(H
2O)
2(
L)](X)
2,respectively. The square-planar complexes [Ni(
L)](X)
2 were obtained by heatin
g these octahedral complexes.Spectrophotometric titrations of [Ni(
L)](BF
4)
2 were performed with neutral and ne
gatively char
ged li
gands. Thecolor of nitromethane solutions of this square-planar complex turns from red to cyan, purple, blue, yellow-
green,and pink followin
g addition of halides, acetonitrile, water, pyridine, and 2,2'-bipyridine, respectively. X-ray structuralanalyses were carried out on the {[Ni(ClO
4)(H
2O)(
L)][Ni(H
2O)
2(
L)]}(ClO
4)
3, [Ni(CH
3CN)(H
2O)(
L)](ClO
4)
2, [{Ni(
L)}
2(
![](/ima<font color=)
ges/entities/m
gr.
gif">
-Cl)
2](ClO
4)
2, and [{Ni(
L)}
2(
![](/ima<font color=)
ges/entities/m
gr.
gif">
-Br)
2]Br
2·2CH
3NO
2 complexes.