Coordination Chemistry Reviews 226 (2002) 199– 209

www.elsevier.com/locate/ccr

Copper(II) complexes with multidentate Schiff-base ligands

containing imidazole groups: ligand-complex or self-complementary
molecule?
Yukinari Sunatsuki, Yuri Motoda, Naohide Matsumoto *
Department of Chemistry, Faculty of Science, Kumamoto Uni6ersity, Kurokami 2 -39 -1, Kumamoto 860 -8555, Japan

Received 12 April 2001; accepted 19 June 2001

Contents

Abstract. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
2. Critical point between ligand-complex and self-complementary molecule: copper(II) complex with a tetradentate ligand containing
an imidazole group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3. Copper(II) complex with tridentate ligands containing an imidazole group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
4. Copper(II) complex with a tetradentate ligand containing two imidazole groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
5. Copper(II) complex with a pentadentate ligand containing two imidazole groups. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
6. Copper(II) complex with a tripod-type ligand containing three imidazole groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209

Abstract

The copper(II) complexes with multidentate Schiff-base ligands containing imidazole groups have potentially donor and
acceptor character in the formation of a coordination bond and a hydrogen bond. They can function as a ligand-complex or as
a self-complementary building block for the construction of the assembly structure due to the formation of a coordination bond
or a hydrogen bond. In such self-complementary complexes, the monomer is stabilized as a protonated species under acidic
conditions, while under appropriate basic conditions the generated imidazolate nitrogen atom coordinates to the Cu(II) ion of the
adjacent unit or hydrogen-bonds to the imidazole group of the adjacent unit to give assembly structures in the crystals, depending
on the ligand framework and the preferred coordination number of the Cu(II) ion. The interconversion between the monomer and
the self-assembled oligomer is reversible by pH adjustment. © 2002 Elsevier Science B.V. All rights reserved.

Keywords: Supramolecular chemistry; Hydrogen bond; Copper(II) complexes

metal complex is especially attractive and useful for the

purpose of the construction of a variety of molecular
1. Introduction structures and functional materials, because a metal ion
together with its ligand contains not only effective
A metal complex is a treasury of functional vectors
structural information to guide the self-assembly reac-
that have the diversity of geometric and electronic
tion but it also contains various functional vectors due
structures; versatile functional materials can be created
to its electronic structure [1–4]. Two types of building
by rational molecular design when the functional vector
block methods using a metal complex, methods I and
accumulates. The self-assembly process involving a
II, have been successful: (1) method I, in which one
kind of metal complex contains simultaneously the
* Corresponding author. Tel./fax: + 81-96-342-3390.
E-mail address: [email protected] (N. Mat-
donor and acceptor ability as a self-complementary
sumoto). molecular building block to construct the assembly

0010-8545/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 1 0 - 8 5 4 5 ( 0 1 ) 0 0 4 1 7 - 9
200 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209

structure [5,6]; (2) method II, in which two kinds of condensation of 4-formylimidazole and N,N-
metal complexes which contain donor and acceptor dimethyldiethylenetriamine 1. Compound 1 reacts with
ability, respectively, are used as molecular building pentamethyldiethylenetriaminecopper(II) and with itself
blocks. Method II has been very successful in creating in the presence of base to give the imidazolate-bridged
molecular-based magnetic materials [7]. species 2 and 3, respectively [8]. Brewer et al. isolated a
In this article, as a representative example of method mono-deprotonated species 4 [9,10]. This complex 4
I, Cu(II) complexes with multidentate Schiff-base lig- functions as a monodentate ligand-complex at the imi-
ands containing imidazole groups are discussed. These dazolate nitrogen atom and reacts with tetraphenylpor-
Cu(II) complexes potentially have both donor and ac- phyrinatoFe(III) to give a linear Cu(II)Fe(III)Cu(II)
ceptor abilities in the formation of coordination bond- complex 5, in which a ferromagnetic interaction be-
ing and hydrogen bonding. Under the acidic condition tween low-spin Fe(III) and Cu(II) ions is observed [11].

of a pH region lower than the dissociation constant of We have synthesized a series of Cu(II) complexes of
the imidazole group, the donor ability at the imidazole the unsymmetrical tetradentate Schiff-base ligands con-
group is inhibited by the proton and no assembly taining an imidazole group per molecule (6–12) and
process occurs. Under an appropriate alkaline condi- examined their self-complementary behavior [12–14].
tion higher than the dissociation constant, the imidazo- The Cu(II) complexes exhibit potentially the following
late nitrogen atom generated coordinates to a Cu(II) building-block characteristics, allowing a simple self-as-
ion of the adjacent unit or hydrogen-bonds to the sembly process: (1) the complex molecule has potential
imidazole group of the adjacent unit to construct the donor ability at the imidazolate nitrogen atom; (2) the
assembly structures. Several factors control the charac- complex molecule has potential acceptor ability at the
teristics of the self-assembly process. An appropriate fifth axial coordination site if it is available; (3) al-
choice of ligand framework may yield a chosen self-as- though the complex molecule has potentially both
sembly structure, due to the independent but additive donor and acceptor coordination abilities, the donor
steric restrictions imposed by the ligand framework and ability is concealed by the imidazole proton in acidic
the preferred coordination number and geometry of the conditions lower than pKd (dissociation constant of
Cu(II) ion upon self-assembly. Here we describe the imidazole proton) where the complex is thus
basic conditions for self-complementary molecules. monomeric; (4) at pH higher than pKd, the donor
ability which triggers the self-assembly process is re-
vealed; (5) since Cu(II) ion prefers either four or five
2. Critical point between ligand-complex and coordination with these tetradentate Schiff-base lig-
self-complementary molecule: copper(II) complex with a ands, only the axial coordination site is available to
tetradentate ligand containing an imidazole group assemble the species; (6) they can be classified into two
types: Type A and Type B complexes, from the depro-
Lippard et al. reported that the Cu(II) complex with tonation behavior and by the strength of the equatorial
the tetradentate Schiff-base ligand formed by the 1:1 ligand field.
 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209 201

Type A: When the ligand field strength of the equato- ligand. The deprotonated complex 12% assumes an imi-
rial tetradentate ligand is strong enough or there is dazolate-bridged one-dimensional (1D) zigzag-chain
steric hindrance to axial coordination, the self-assembly structure [18]. The self-assembly process from monomer
reaction does not occur. Such a deprotonated complex to imidazolate-bridged 1D zigzag chain is schematically
would exist as a monomer and behaves as a ligand- shown in Fig. 2.
complex like Brewer’s complex 4. As shown in Fig. 1,
the ligand-complex 6 coordinates to another metal
complex exhibiting a vacant and/or substitutable coor- 3. Copper(II) complexes with tridentate ligands
dination site to give a series of imidazolate-bridged containing an imidazole group
homo- and hetero-metal polynuclear complexes, whose
magnetic properties were extensively investigated [15– Copper(II) complexes with tridentate ligands con-
25]. taining an imidazole group formed by the 1:1 condensa-
Type B: When the ligand field strength of the equato- tion of 2-methyl-4-formylimidazole (or 2-phenyl-4-
rial tetradentate ligand is sufficiently weak and the formylimidazole) and 2-aminoethylpyridine, 13 and 14,
complex has acceptor ability to receive the imidazolate are representative molecules which show pH-dependent
nitrogen atom of the adjacent unit at the axial coordi- reversible interconversion between monomer and
nation site, the self-assembly reaction is motivated by oligomer [26]. Compounds 13 and 14 with the chemical
the deprotonation of the imidazole group and the self- formula [CuCl2(HL)] (HL = N-(2-methyl or phenyl-imi-
assembly compound is formed. For example, the proto- dazol-4-ylmethylidene)-2-aminoethylpyridine) assume a
nated Cu(II) complex 12 exists as a monomer and pentacoordinated geometry with a N3Cl2 donor set in
assumes a square-planar coordination geometry with the solid state. The CuCl(1) and CuCl(2) distances
the N3O donor atoms of the tetradentate Schiff-base are 2.293(1) and 2.581(1) A, for 13, and 2.2679(5) and

Fig. 1. Reaction scheme of 6 as a ligand-complex with the other metal complexes.

202 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209

Fig. 2. Schematic representation for the self-assembly reaction of 12.

2.5184(6) A, for 14, respectively. In the solid state two lamine or NaOH in aqueous solution, condensation
Cl− anions are bound to the Cu(II) ion, but there are occurred through formation of coordination bonds be-
no CuCl bonds in aqueous solution where water tween the imidazolate nitrogen atoms and Cu(II) ions,
molecules instead of Cl− are coordinated to Cu(II). yielding the self-assembled cyclic tetranuclear and hex-
Since the three equatorial coordination sites are occu- anuclear compounds 13% and 14%, in which each Cu(II)
pied by the N3 donor atoms of the tridentate ligand and ion is coordinated by the three nitrogen donor atoms
the coordinated water molecule is easily substituted, the from the tridentate ligand and the imidazolate nitrogen
fourth equatorial site can be used for the assembly of the adjacent unit. Fig. 3 shows the assembly reaction
reaction. When the protonated complexes 13 and 14 from monomer to oligomer, together with the sche-
were treated with an equimolar amount of triethy- matic representation by a molecular brick.

Fig. 3. Schematic representation of the self-assembly reaction for Cu(II) complexes with tridentate ligands containing an imidazole group, 13 and
14.
 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209 203

There are no relevant differences in the four CuN ings (Fig. 4) clearly show that the presence of bulky
coordination bond distances and imidazolate-bridged phenyl substituents does not allow a cyclic tetranuclear
CuCu distances between the two oligomeric structures. structure for steric reasons. The structural parameter
Among these four CuN bonds, the shortest involves determining the nuclearity is the NCuN angle in the
the imidazolate nitrogen atom occupying the equatorial (CuIm)n - macrocyclic framework. Thus, the NCuN
coordination site of the adjacent Cu(II) ion. The 2-imi- angle in the 13% cyclic tetramer is substantially smaller
dazolate substituents of the adjacent modular units than in the cyclic hexamer 14%.
orient themselves in directions opposite to each other to The reversible interconversion between the Cu(II)
form the imidazolate-bridged cyclic structure. Thus, the monomer and cyclic oligomer has been confirmed by
2-imidazole substituents of the next nearest neighboring potentiometric pH titration and pH-dependent elec-
units face each other. Therefore, concerning the strong tronic spectra. Fig. 5(a) shows the results of forward
coordination bonds resulting from the imidazolate- and reverse titrations carried out in water at 25 °C.
bridges and the cyclic structure, the steric repulsion Fig. 5(b) shows the pH-dependent electronic spectra for
between 2-imidazolate substituents facing each other is the 13“ 13% forward conversion. In Fig. 5(a), the degree
the factor determining the orientation of adjacent mod- of proton association n decreases from 1 to 0 for the
ular units, and consequently the actual structure. A forward titration and increases from 0 to 1 for the
cyclic hexanuclear structure is more favorable for the reverse titration. The forward and reverse titration
bulky 2-phenyl substituent than a cyclic tetranuclear curves are almost the same, indicating that the deproto-
structure to avoid steric repulsion, because the CuCu nation and protonation are reversible. In Fig. 5(b), the
distance of similarly oriented modular units is increased spectrum of 13 exhibits a broad band at 682 nm (molar
in a cyclic hexanuclear structure. The space-filled draw- extinction coefficient m= 48 M − 1 cm − 1) assignable to a

Fig. 4. Space-filling representations of cyclic tetranuclear 13% (left) and hexanuclear 14% (right) complex molecules, showing the cavity and the
orientation of 2-imidazolate substituents.

Fig. 5. (a) pH-Dependent potentiometric titration curves (proton association degree n vs. pH) for the forward (black) and reverse (white) titrations
of 13. (b) pH-Dependent electronic spectra of 13 for the forward titration procedure. A spectrum was recorded after each 0.4 ml addition of a
0.1 M NaOH solution, until 1 equiv. of NaOH was added.
204 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209

d –d transition. On adding a 0.1 M aqueous NaOH bility [29]. We have modified the complex slightly by the
solution, this broad band shifts to lower wavelength use of 6-methyl-2-carboxypyridine, instead of 2-
and the molar extinction coefficient increases. When the pyridinecarboxyaldehyde, 18. The deprotonation reac-
amount of NaOH solution added was equimolar, the tion of 18 gave the imidazolate-bridged cyclic hexamer
spectrum generated had a d– d band maximum at 620 18%. The complex showed pH-dependent reversible inter-
nm (m = 127 M − 1 cm − 1), perfectly consistent with the conversion between monomer 18 and cyclic hexamer 18%
spectrum of 13%. This spectral change is characterized [30]. The corresponding Pd(II) complex with the same
by an isosbestic point at 805 nm, typical of an equi- ligand produced a cyclic tetranuclear structure under
librium between the protonated and deprotonated deprotonation, showing that the nuclearity depends on
forms. The spectra for the 13% “13 reverse titration the metal ion. The disassembly process also depends on
exhibit an isosbestic point at the same wavelength and the metal ion, since the Cu(II) complex exhibits a
reach the genuine spectrum of 13. The reversibility is reversible interconversion, whereas the Pd(II) complex
achieved owing to the coordination plasticity of Cu(II). did not show a perfect disassembly process [28].

Coracio et al. synthesized the analogous Cu(II) com- 4. Copper(II) complex with a tetradentate ligand
plex with the tridentate ligand formed by the 1:1 con- containing two imidazole groups
densation product of 2-formylimidazole and
2-aminoethylpyridine, 15 [27,28]. The Cu(II) complex Copper(II) complexes with N,N%-bis(2-substituted-
15 is different from 13 and 14 in that the tridentate imidazol-4-ylmethylidene)-1,4-diaminobutane (2-sub-
ligand of 15 is derived from 2-formylimidazole, instead stituent=H, 19; Me, 20) were synthesized [31]. X-ray
of 4-formylimidazole. The self-assembly structure of the analyses of 19 and 20 revealed that the molecules
deprotonated compound 15% is an imidazolate-bridged assume a butterfly shape bent by a line of
1D structure, which is quite different from the cyclic N(2)CuN(4) where the angle of N(3)CuN(5) repre-
structures of 13% and 14%. Further, compound 15 reacts senting the extent of the molecular bend is 150.9(2) and
with hfac− under alkaline conditions and the presence 105.66(8) for 19 and 20, respectively. Due to the molec-
of excess M(hfac)2 to give a trinuclear compound 16. ular bend, two imidazole moieties (sites A and B) are

Nakao et al. synthesized the Cu(II) complex with the recognized as two inequivalent groups for the deproto-
tridentate ligand formed by the 1:1 condensation of nation process in which the imidazole group of site A is
histamine and 2-pyridinecarboxyaldehyde, 17. The de- in an equatorial CuN3 plane, while that of site B is in a
protonation reaction of 17 gave an imidazolate-bridged CuN2 plane bent from the equatorial coordination
tetranuclear compound 17%, whose structure was sug- plane. The assembly process is illustrated in Fig. 6.
gested by the temperature-dependent magnetic suscepti- Compound 19 dissociates first a proton from site B to
 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209 205

Fig. 6. Schematic representation of the self-assembling reaction for Cu(II) complexes with tetradentate ligands containing two imidazole groups,
19 and 20.

give an infinite zigzag-chain compound 19%, while 20 Coracio et al. also reported a copper(II) complex
dissociates first a proton from site A to give a cyclic-te- with a tetradentate ligand containing two imidazole
tranuclear compound 20%. Compound 20% undergoes groups, 21, in which 2-formylimidazole is used instead
further deprotonation to give an electrically neutral of 2-substituted-4-formylimiazole [32,33]. The deproto-
di-deprotonated complex 20¦. The larger bend found in nation reaction of 21 gave an imidazolate-bridged 1D
20, 20%, and 20¦ is ascribed to the steric repulsion compound 21%, in which the N4 coordination basal
between two 2-methyl-imidazole moieties. Owing to a plane is almost planar and the imidazolate nitrogen
nearly perpendicular bend for 20, the distance of atom of the adjacent unit occupies the axial position
CuN(5) = 2.125(2) A, of site B is substantially longer with the CuN distance of 2.214(9) A, . Compound 21
than that of CuN(2) = 1.979(2) A, of site A, implying also reacts with Ni(hfac)2 to give trinuclear (R=H, 22)
that the imidazole proton at N(1) of site A would and dinuclear (R= OH, 23) compounds.
dissociate first. The imidazolate nitrogen atom occupies
one of the equatorial coordination sites of the adjacent
block to give a cyclic tetramer. On the other hand, due
to the spread-out shape of 19, the distance of 5. Copper(II) complexes with a pentadentate ligand
CuN(2) =1.959(3) A, is rather compatible with that of containing two imidazole groups
CuN(5) = 1.998(4) A, ; in fact, the imidazole proton of
site B dissociates first and the imidazolate nitrogen The protonated copper(II) complexes of the strand-
atom, N(6), occupies an apical position of the adjacent type pentadentate Schiff-base ligands containing two
molecule to give an infinite chain. imidazole groups, 24–28, were synthesized in our labo-
206 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209

ratory [34,35]. When 2 equiv. of triethylamine was …CACA… syndiotactic 1D zigzag chains. In the for-
added to the 1:1 mixed-solution of the ligand and mer compounds, two adjacent methyl or H groups at
Cu(II) perchlorate hexahydrate in methanol, the mono- the 2-position connected by hydrogen bonds arrayed in
deprotonated complexes 24% – 28% were obtained as green the same direction, thus allowing homochiral aggrega-
crystals. The mono-deprotonated Cu(II) complexes tion of the complex molecules in a 1D chain. On the
24% – 28% involves protonated (imidazole) and deproto- other hand, in 27% and 28%, two adjacent bulky phenyl
nated (imidazolate) moieties per molecule, in which the groups require opposite orientations in order to avoid
CuN distance of the protonated moiety is substantially steric hindrance indicated by the space filling represen-
longer than that of the deprotonated moiety, as exem- tation (Fig. 8), thus allowing heterochiral aggregation.
plified by the bond distances of 2.354(6) and 2.000(6) A, Enantioselective aggregation with homochirality or het-
for 25%. Due to the spiral coordination arrangement of erochirality can thus be controlled with suitable sub-
the achiral strand-type ligand, the Cu(II) complex be- stituents. This assembly reaction involves a process
comes a chiral molecule with C (clockwise) and A from the synthetically simple achiral ligand and a
(anticlockwise) enantiomers. The mono-deprotonated Cu(II) ion, to the isolated chiral complex, and then to
complex functions as a chiral self-complementary build- the homochiral and heterochiral 1D zigzag chain. The
ing component and aggregates possibly into heterochi- process is schematically drawn in Fig. 9.
ral (…CACA…) or homochiral (…CCCC… and
…AAAA…) 1D zigzag chains, due to intermolecular
imidazole–imidazolate hydrogen bonds. The chemical 6. Copper(II) complexes with a tripod-type ligand
structures, the enantiomers, and homochiral and hete- containing three imidazole groups
rochiral 1D structures constructed by the imidazole–
imidazolate hydrogen bond are drawn in Fig. 7. A copper(II) complex with a hexadentate tripod-type
The crystal lattice of 24%, 25%, and 26% yielded either ligand involving three imidazole groups, 29, induces a
…CCCC… or …AAAA… isotactic 1D zigzag chains, chirality of C and A enantiomers due to the screw
while the crystal lattices of 27% and 28% yielded coordination arrangement of the tripod-type ligand

Fig. 7. (a) Molecular structures of copper(II) complexes 24– 28 with the pentadentate ligands. (b) Structures of C (clockwise) and A (anticlockwise)
enantiomers. (c) Two possible 1D structures of the mono-deprotonated complex formed by hydrogen bonds between two adjacent enantiomers,
homochiral (upper) and heterochiral (lower) 1D zigzag chains. Here, C and A enantiomers represent green and red color, respectively. The same
color representation is also used in following figures.
 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209 207

Fig. 8. CHARON drawings and the space filling representations of the two adjacent molecules linked by the hydrogen bond for 26% (left) and 27%
(right).

Fig. 9. Schematic representation of the hydrogen bonding self-assembling reaction for Cu(II) complexes with pentadentate ligands containing two
imidazole groups, 24 – 28.

Fig. 10. (a) Molecular structures of [Cu(H3L)]2 + . (b) Views looking down and up the molecule along the molecular C3 axis for C and A
enantiomers and their schematic representations, in which the curve line from the central tertiary amine to the terminal imidazole nitrogen through
the imine nitrogen is represented by arrows.
208 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209

Fig. 11. Two pairs of plausible homochiral and heterochiral assemblies for the hemi-deprotonated complex formed by intermolecular
imidazole– imidazolate hydrogen bonds. (a) and (b) show a pair of homochiral and heterochiral structures with trigonal void. (c) and (d) show
another pair of homochiral and heterochiral structures with hexagonal void.

Fig. 12. Chiral two-dimensional structure constructed by hydrogen bonds for 29% (left) and a side-view showing layer structure (right). Red colored
molecule in CHARON drawing represents A enantiomer.

around the metal ion as shown in Fig. 10 [36,37]. The ral molecules. The X-ray analysis demonstrated that the
hemi-deprotonated species generated in appropriate ba- separation of the two enantiomers spontaneously oc-
sic conditions, 29%, functions as a chiral self-comple- curred during the course of the crystallization.
mentary double-faced H-bonding recognition unit and
forms a two-dimensional (2D) extended structure due
to the intermolecular imidazole– imidazolate hydrogen 7. Summary
bond. As shown in Fig. 11, there are four possible
structures for a 2D layer (a– d). Among them, only the Copper(II) complexes with multidentate Schiff-base
structure (a) with homochiral aggregation and trigonal ligands containing imidazole groups have been studied.
void has been so far obtained. The CHARON drawing These complexes potentially have both donor and ac-
for the 2D structure of 29% is shown in Fig. 12. The ceptor abilities to function as self-complementary build-
generated 2D structure is a chiral layer constructed by ing blocks for the construction of assembly structures
homochiral aggregation, in which the C isomer aggre- or to function as a ligand-complex. In such self-comple-
gates only with the C isomer and the A isomer aggre- mentary complexes, the monomer is stabilized as a
gates only with the A isomer to produce a chiral 2D protonated species under acidic conditions, while under
structure. Further, the layers with the same chirality are appropriate basic conditions the imidazolate nitrogen
stacked to form a chiral crystal consisting of homochi- atom generated coordinates to the metal ion of the
 Y. Sunatsuki et al. / Coordination Chemistry Re6iews 226 (2002) 199–209 209

adjacent unit or hydrogen-bonds to the imidazole [8] R.N. Katz, G. Kolks, S.J. Lippard, Inorg. Chem. 19 (1980) 3845.
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1669.
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