Systematic Synthesis of Di-, Tri-, and Tetranuclear Homo- and Heterometal Complexes Using a Mononuclear Copper Synthon with a Tetradentate Amino Alcohol Ligand

Article abstract of DOI:10.1002/ejic.201600142

The reaction of Cu(NO₃)₂·3H₂O with an N₂O₂tetradentate amino alcohol, N,N-dibenzyl-N′,N′-bis(2-hydroxyethyl)ethylenediamine (H₂L), afforded the mononuclear copper complex [Cu(H₂L)(NO₃)](NO₃) (1), which has been used to construct a series of di-, tri-, and tetranuclear homo- and heterometallic complexes. Complex 1 dimerized in the presence of NEt₃to form the Cu₂complex [Cu₂(HL)₂](NO₃)₂(2) by the deprotonation of one of the two hydroxy groups in the H₂L ligand. The reaction of 1 with Cu(OCOH)₂in the presence of NEt₃afforded the Cu₃complex [Cu₃(HL)₂(OCOH)₂](NO₃)₂(5). The metalloligand {Cu(HL)}⁺derived from 1 reacted with M(OAc)₂(M = Cu, Co, Zn, Ni) in the absence of NEt₃to form the asymmetric CuM dinuclear complexes [CuM(HL)(OAc)(NO₃)₂] [M = Cu (3a), Co (3b), Zn (3c), Ni (3d)], whereas in the presence of NEt₃a unit of M(OAc) was captured by two metalloligands to give the bent CuMCu trinuclear complexes [Cu₂M(HL)₂(OAc)₂(NO₃)](NO₃) [M = Cu (4a), Co (4b), Mn (4c)], which were further transformed into the linear CuMCu trinuclear complexes [Cu₃(HL)₂{(PhO)₂PO₂}₂](NO₃)₂(7a) and [Cu₂M(HL)₂{(PhO)₂PO₂}₂(MeOH)₂](NO₃)₂[M = Co (7b), Mn (7c)] with the aid of diphenyl phosphate bridging ligands. When (PhO)PO₂(OH) was used as an auxiliary bridging ligand in the reaction of 1 with M(OAc)₂and NEt₃, the Cu₂M₂tetranuclear complexes [Cu₂M₂(HL)₂{(PhO)PO₃}₂(NO₃)₂] [M = Co (8a), Zn (8b)] were synthesized. These results demonstrate that the mononuclear copper synthon with the N₂O₂tetradentate amino alcohol ligand {Cu(H₂L)}²⁺generates the quite useful metalloligand {Cu(HL)}⁺by the deprotonation of a hydroxy group, and subsequent reactions lead to the construction of a series of homo- and heterometal complexes containing Cu₂, CuM (M = Cu, Co, Zn, Ni), bent-CuMCu (M = Cu, Co, Mn), linear-CuMCu (M = Cu, Co, Mn), and Cu₂M₂(M = Co, Mn) cores in a systematic and selective manner.

Full text of DOI:10.1002/ejic.201600142

DOI: 10.1002/ejic.201600142
Full Paper
Amino Alcohol Ligands
Systematic Synthesis of Di-, Tri-, and Tetranuclear Homo- and
Heterometal Complexes Using a Mononuclear Copper Synthon
with a Tetradentate Amino Alcohol Ligand
Takayuki Nakajima,*[a] Chisako Yamashiro,[a] Megumi Taya,[a] Bunsho Kure,[a] and
Tomoaki Tanase*[a]
Abstract: The reaction of Cu(NO3)2·3H2O with an N2O2 tetra- Cu (4a), Co (4b), Mn (4c)], which were further transformed into
the linear CuMCu trinuclear complexes [Cu3(HL)2{(PhO)2PO2}2]-
(NO3)2 (7a) and [Cu2M(HL)2{(PhO)2PO2}2(MeOH)2](NO3)2 [M = Co
(7b), Mn (7c)] with the aid of diphenyl phosphate bridging li-
gands. When (PhO)PO2(OH) was used as an auxiliary bridging
ligand in the reaction of 1 with M(OAc)2 and NEt3, the Cu2M2
tetranuclear complexes [Cu2M2(HL)2{(PhO)PO3}2(NO3)2] [M = Co
(8a), Zn (8b)] were synthesized. These results demonstrate that
the mononuclear copper synthon with the N2O2 tetradentate
amino alcohol ligand {Cu(H2L)}2+ generates the quite useful
metalloligand {Cu(HL)}+ by the deprotonation of a hydroxy
group, and subsequent reactions lead to the construction of a
series of homo- and heterometal complexes containing Cu2,
CuM (M = Cu, Co, Zn, Ni), bent-CuMCu (M = Cu, Co, Mn), linear-
CuMCu (M = Cu, Co, Mn), and Cu2M2 (M = Co, Mn) cores in a
systematic and selective manner.
dentate amino alcohol, N,N-dibenzyl-N′,N′-bis(2-hydroxy-
ethyl)ethylenediamine (H2L), afforded the mononuclear copper
complex [Cu(H2L)(NO3)](NO3) (1), which has been used to con-
struct a series of di-, tri-, and tetranuclear homo- and heterome-
tallic complexes. Complex 1 dimerized in the presence of NEt3
to form the Cu2 complex [Cu2(HL)2](NO3)2 (2) by the deprotona-
tion of one of the two hydroxy groups in the H2L ligand. The
reaction of 1 with Cu(OCOH)2 in the presence of NEt3 afforded
the Cu3 complex [Cu3(HL)2(OCOH)2](NO3)2 (5). The metallo-
ligand {Cu(HL)}+ derived from 1 reacted with M(OAc)2 (M = Cu,
Co, Zn, Ni) in the absence of NEt3 to form the asymmetric CuM
dinuclear complexes [CuM(HL)(OAc)(NO3)2] [M = Cu (3a), Co
(3b), Zn (3c), Ni (3d)], whereas in the presence of NEt3 a unit of
M(OAc) was captured by two metalloligands to give the bent
CuMCu trinuclear complexes [Cu2M(HL)2(OAc)2(NO3)](NO3) [M =
Introduction
ively.[3] There are many examples of metal complexes with N2O2
tetradentate Schiff-base and N2S2 aminothiolate ligands that
have been used as metalloligands to synthesize heterometal
complexes.[4] However, amino alcohol based metalloligands are
limited to a few examples incorporating N-glycosyl polyamines
and aminophenol ligands,[5] in spite of the fact that N-alkylated
diethanolamine ligands (Scheme 1, a) are widely used for the
synthesis of polynuclear metal complexes by one-pot self-as-
sembly methods.[6–9] The two alkoxide units formed in N-alkyl-
ated diethanolamine ligands by the deprotonation of the
hydroxy groups under basic reaction conditions are able to
bridge two or three metal ions to construct polynuclear com-
plexes. In this regard, when mononuclear complexes supported
by N-alkylated diethanolamine ligands in the diprotonated form
are stabilized, they must be feasible metalloligands for the syn-
thesis of heterometallic complexes due to the preserved bridg-
ing ability through deprotonation of two hydroxy groups. With
the aim of exploring new metalloligands, we have synthesized a
new N2O2 tetradentate amino alcohol, N,N-dibenzyl-N′,N′-bis(2-
hydroxyethyl)ethylenediamine (H2L; Scheme 1, b), to stabilize
divalent mononuclear complexes with the {M(H2L)}2+ synthon
by introducing an extra nitrogen donor into the N-alkylated
diethanolamine.
The rationally designed synthesis of polynuclear transition-
metal complexes with intriguing topological structures is of
substantial importance in inorganic chemistry because of their
diverse applications as catalysts and in electronic, photochemi-
cal, and magnetic devices as well as in biological systems.[1]
There are several strategies for synthesizing polynuclear metal
complexes, including an approach involving the use of the so-
called “metalloligands” as inorganic synthons, in other words, a
method in which a complex of the M ion with a rationally de-
signed multidentate ligand is bound to another metal ion M′
by virtue of the bridging ability of the ligand.[2] In particular, the
method is valuable for the synthesis of heterometal complexes,
because one-pot syntheses based on self-assembly do not al-
ways afford the desired heterometal MM′ complexes select-
[a] Department of Chemistry, Faculty of Science, Nara Women's University,
Kitauoya-nishi-machi, Nara 630-8506, Japan
E-mail: t.nakajima@cc.nara-wu.ac.jp
tanase@cc.nara-wu.ac.jp
http://www.chem.nara-wu.ac.jp/~tanase/TanaseGroup/
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejic.201600142.
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mononuclear {Cu(H2L)}2+ synthon seems to be a useful metallo-
ligand for constructing multinuclear complexes through the de-
protonation of the two hydroxy groups, as evidenced by its
transformation into di- and trinuclear copper(II) complexes (see
below).
Scheme 1. Structures of (a) N-alkylated diethanolamine and (b) H2L.
In this study, a mononuclear copper(II) complex with the H2L
ligand was prepared and characterized as [Cu(H2L)(NO3)](NO3)
(1) containing two hydroxy groups. Complex 1 was found to be
an effective metalloligand for the construction of a variety of
di-, tri-, and tetranuclear homo- and heterometal complexes 2–
8
with the assistance of auxiliary bridging ligands:
[Cu2(HL)2](NO3)2 (2), [CuM(HL)(OAc)(NO3)2] (3: M = Cu, Co, Zn,
Ni), [Cu2M(HL)2(OAc)2(NO3)](NO3) (4: Cu, Co, Mn),
M
=
[Cu3(HL)2(OCOH)2](NO3)2 (5), [Cu2M(HL)2{(PhO)2PO2}2(MeOH)n]-
(NO3)2 (7: n = 0, M = Cu; n = 2, M = Co, Mn), and
[Cu2M2(HL)2{(PhO)PO3}2(NO3)2] (8: M = Co, Zn). Their systematic
synthesis and characterization are described with a focus on the
flexible mononuclear synthon {Cu(HL)}+ as a new metalloligand.
Figure 1. ORTEP diagram of the complex cation of 1 with the atomic number-
ing scheme. The thermal ellipsoids are drawn at the 40 % probability level,
and the C–H hydrogen atoms have been omitted for clarity.
When complex 1 was treated with 1.5 equiv. of NEt3, the
dinuclear copper complex [Cu2(HL)2](NO3)2 (2) was obtained in
80 % yield (Scheme 2). The structure of 2 (Figure 2 and Table S8
in the Supporting Information) has a crystallographically im-
posed inversion center and is comprised of a [Cu2O2] rhombic
core supported by two HL– ligands. The copper ions exhibit a
slightly distorted square-pyramidal geometry (τ = 0.10) with the
O2 oxygen atom occupying the apical site. The Cu–O and Cu–
N distances involved in the basal plane range from 1.917(1) to
2.049(1) Å, whereas the axial Cu–O2 bond is elongated
[2.310(2) Å]. The N2O2 ligand exists in the mono-deprotonated
form HL– with the alkoxo O1 atom bridging two copper ions
[Cu···Cu 2.991(1) Å, Cu–O1 1.953(1) Å, Cu*–O1 1.917(1) Å, Cu–
O1–Cu* 101.22(5)°, O1–Cu–O1* 78.78(5)°] to form the [Cu2O2]
plane, which is usually observed in dinuclear complexes sup-
ported by N-alkylated diethanolamine ligands.[6h,7c,12] The axial
Results and Discussion
Synthesis of [Cu(H2L)(NO3)](NO3) (1) and Its
Transformation into Cu2 and Cu3 Complexes
The N2O2 tetradentate ligand H2L (Scheme 1, b) was synthe-
sized in good yield by the reaction of N,N-dibenzyl-2-chloro-
ethanamine hydrochloride with 2,2′-iminodiethanolamine in
the presence of Na2CO3 at reflux in acetonitrile.
The reaction of H2L with 1 equiv. of Cu(NO3)2·3H2O in MeOH
at room temperature afforded blue crystals formulated as
[Cu(H2L)(NO3)](NO3) (1) in 86 % yield. The structure of 1 was
determined by X-ray crystallography (Figure 1 and Table S7 in
the Supporting Information). The geometry around the copper
ion is distorted square-pyramidal (trigonal-bipyramidal distor-
tion parameter, τ = 0.37)[10a] with the O2 hydroxy oxygen occu-
pying the apical site and the hydroxy O1, the amino nitrogen
N1 and N2 atoms of H2L, and a nitrate oxygen atom O3 forming
the basal plane. According to the classification of the coordina-
tion mode of the nitrate ion utilizing two parameters, the differ-
ence between the two M–Onitrate bond lengths (Δd) and the
M–O–N bond angles (Δθ),[10b] the nitrate coordinates to the Cu
ion through the O3 oxygen atom [Cu–O3 1.852(2) Å, Cu···O5
2.762(4) Å] in monodentate mode (Δd = 0.910 Å, Δθ = 45.6°).
The N2O2 ligand surrounds the copper center in a tetradentate
coordination mode in the diprotonated form H2L: Cu–N1
1.880(3) Å, Cu–O2 2.097(2) Å, Cu–N2 2.187(2) Å, and Cu–O1
2.232(3) Å. The O1 and O2 hydroxy groups are involved in two
–
hydrogen bonds to the NO3 counter ion [O1···O7 2.741(4),
O2···O6* 2.846(4) Å] to form a 1D network chain (see Figure S1
in the Supporting Information). It should be noted that the di-
protonated form observed in 1 is relatively rare in the case of N-
substituted diethanolamine ligands,[9g,11] and consequently the
Scheme 2. Structure of 1 and its transformation into [Cu2(HL)2](NO3)2 (2) and
[Cu3(HL)2(OCHO)2](NO3)2 (5).
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–
O2 hydroxy group is involved in a hydrogen bond to a NO3
counter ion [O2···O3 2.715(2) Å].
triethanolamine),[13] and related linear tricopper complexes
with the Cu3(μ-alkoxo)2(η1,η1,μ2-acetate)2 core have also been
reported.[13,14] It should be noted that similar reactions with
other metal salts such as M(OCHO)2 (M = Co, Mn, Ni) did not
afford the corresponding mixed-metal trinuclear complexes.
Synthesis of the CuM and CuMCu Homo- and Heterometal
Complexes [CuM(HL)(OAc)(NO3)2] (3: M = Cu, Co, Zn, Ni)
and [Cu2M(HL)2(OAc)2](NO3)2 (4: M = Cu, Co, Mn) from 1
The treatment of 1 with 1 equiv. of M(OAc)2 (M = Cu, Co, Zn,
Ni) in the absence of NEt3 in MeOH at room temperature af-
forded the dinuclear complexes [CuM(HL)(OAc)(NO3)2] [M = Cu
(3a), Co (3b), Zn (3c), Ni (3d)] in yields of 67–90 % (Scheme 3).
The crystal structures of 3a–3d are isomorphous and consist of
a CuM heterodimetallic core supported by a mono-deproto-
Figure 2. ORTEP diagram of 2 with the atomic numbering scheme. The ther-
mal ellipsoids are drawn at the 40 % probability level, and the C–H hydrogen
atoms have been omitted for clarity. Hydrogen bonds are shown as dashed
lines (O2–O3 and O2*–O3*).
–
nated HL– ligand, one acetate, and two NO3 ions (see Figure 4
for 3b and Figures S2–S4 in the Supporting Information for 3a,
3c, and 3d). The geometry around the Cu1 atom is distorted
square-pyramidal (τ = 0.29 for 3a–3c, 0.30 for 3d) with the
hydroxy O2 atom in the axial position [Cu1–O2 2.282(2) Å (3a),
2.290(2) Å (3b), 2.294(2) Å (3c), 2.319(3) Å (3d)]. The distances
to the basal donors (O1, O3, N1, N2) fall in the normal range
of 1.928(2)–2.051(2) Å (3a), 1.918(2)–2.059(2) Å (3b), 1.915(2)–
2.053(2) Å (3c), and 1.912(2)–2.059(2) Å (3d). The M2 centers
adopt a highly distorted octahedral geometry with six M2–O
distances of 1.887(1)–2.503(2) Å (3a), 1.938(1)–2.252(2) Å (3b),
1.925(2)–2.369(3) Å (3c), and 1.941(2)–2.113(4) Å (3d). Two
nitrate anions chelate the M2 ion asymmetrically, with each
having one short and one long bond. The two nitrate ions in
3a [(Δd, Δθ) = (0.492–0.526 Å, 22.1–23.7°)][10b] are anisodentate
due to a Jahn–Teller effect at the Cu2 center, whereas those in
3b–3d [(Δd, Δθ) = (0.001–0.298 Å, 0.3–13.0°)] are bidentate.[10b]
The mono-deprotonated HL– ligand bridges the two metal cen-
ters in a structure similar to that in 2. The Cu1 and M2 ions are
bridged by the alkoxo O1 atom of the HL– ligand and an acetate
in η1,η1,μ2 mode and span 3.3713(4) Å (3a), 3.3850(4) Å (3b),
3.353(1) Å (3c), and 3.398(1) Å (3d) with Cu1–O1–M2 =
124.17(8)° (3a), 122.76(7)° (3b), 121.71(8)° (3c), and 123.7(1)°
(3d). Several examples of related asymmetric dinuclear copper
complexes with the Cu2(μ-alkoxo)(η1,η1,μ2-carboxylate) unit
have been reported.[15] However, mixed-metal dinuclear com-
plexes CuM (M = Co, Zn, Ni) are limited to a few examples,
and in all cases the two metal centers are triply bridged by (μ-
alkoxo)2(η1,η1,μ2-carboxylate) or (μ-alkoxo)(η1,η1,μ2-carboxyl-
ate)2 units.[16]
The reaction of 1 with 1 equiv. of Cu(OCHO)2·4H2O in the
presence of NEt3 resulted in the formation of the linear Cu3
complex [Cu3(HL)2(OCHO)2](NO3)2 (5) in 90 % yield (Scheme 2).
The structure of 5 was revealed by X-ray crystallography (Fig-
ure 3 and Table S11 in the Supporting Information) to possess
a crystallographically imposed inversion center at the Cu2 atom.
The Cu2 center adopts an axially elongated octahedral geome-
try with the μ-alkoxide O1 (O1*) and bridging formate O4 (O4*)
atoms located in the equatorial plane [Cu2–O1 1.932(1), Cu2–
O4 1.965(2) Å]. The axial positions are weakly occupied by the
O7 (O7*) atoms of nitrate anions [Cu2···O7 2.732(2) Å], which
are also involved in hydrogen bonding with the hydroxy O2
(O2*) oxygen atoms of HL– [O2···O7 2.692(2) Å]. The Cu1 ion
exhibits square-pyramidal geometry (τ = 0.19) with the proto-
nated O2 atom in the axial position. The apical Cu1–O2 bond
length of 2.280(2) Å is longer than those to the basal donor
atoms [Cu–O1 = 1.948(1) Å, Cu–O3 1.949(2) Å, Cu–N1 2.004(2) Å,
Cu–N2 2.078(1) Å]. The HL– ligand coordinates to two copper
ions similarly to 2. The core structure of Cu3(μ-alkoxo)2(η1,η1,μ2-
formate)2 has been observed in [Cu3(OCOH)4(TEAH2)2] (TEAH3 =
When 1 was treated with 1 equiv. of M(OAc)2 (M = Cu, Co,
Mn) in the presence of NEt3 in MeOH at room temperature, the
CuMCu trinuclear complexes [Cu2M(HL)2(OAc)2](NO3)2 [M = Cu
(4a), Co (4b), Mn (4c)] were obtained selectively in yields of 90,
80, and 93 % (with respect to 1), respectively. When the ratio
of M(OAc)2 (M = Cu, Co, Mn) was reduced to 0.5 equiv., 4a–c
were isolated in lower yields although the reasons for this are
not yet clear.
Figure 3. ORTEP diagram of 5 with the atomic numbering scheme. The ther-
mal ellipsoids are drawn at the 40 % probability level, and the C–H hydrogen
atoms and phenyl rings have been omitted for clarity. Hydrogen bonds are
shown as dashed lines (O2–O7 and O2*–O7*).
The crystal structures of 4a–4c are isomorphous and com-
prised of a trinuclear Cu2M core supported by two mono-de-
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125.32(2)° (4b), 124.60(3)° (4c)]. The Cu1···M2 distances
[3.523(2)–3.569(1) Å] are significantly longer than those of
Cu1*···M2 [3.3085(8)–3.455(1) Å], which is related to the larger
angles of O4–C21–O6 [122.7(4)–124.0(3)°] and Cu1–O1–M2
[120.3(5)–124.1(3)°] compared with those of O4–C21–O5
[120.8(5)–122.4(4)°] and Cu1*–O3*–M2 [108.3(1)–110.0(1)°].
Scheme 3. Preparation of [CuM(HL)(OAc)(NO3)2] (3: M = Cu, Co, Zn, Ni) and
[Cu2M(HL)2(OAc)2](NO3)2 (4: M = Cu, Co, Mn) from 1.
Figure 5. ORTEP diagram of 4c with the atomic numbering scheme. The ther-
mal ellipsoids are drawn at the 40 % probability level, and the C–H hydrogen
atoms and phenyl rings have been omitted for clarity. Hydrogen bonds are
shown as dashed lines (O3–O10* and O2*–O10*).
The environment around the Cu1 center is similar to those
observed in 3a–3c, but it has a distorted trigonal-bipyramidal
geometry [τ = 0.61 (4a), 0.65 (4b), 0.68 (4c)] with the O4 and
N1 atoms occupying the axial sites. The bond lengths involving
the Cu1 atom are in the normal range of 1.913(3)–2.120(4) Å
(4a), 1.921(3)–2.117(3) Å (4b), and 1.916(2)–2.119(2) Å (4c). The
M2 ions exhibit slightly distorted octahedral structures with six
M2–O bond lengths of 1.906(6)–2.406(7) Å (4a), 1.967(5)–
2.337(5) Å (4b), and 1.973(11)–2.363(5) Å (4c), and they are con-
nected to the two Cu ions through two η1,η1,μ2-acetate and
two alkoxides of HL–. The O7 and O8 atoms of a nitrate are
bound to the M2 ion in bidentate fashion [(Δd, Δθ) = (0.010–
0.170 Å, 2.5–7.8°)].[10b]
Although several examples of bent trinuclear copper com-
plexes with Cu3(μ-alkoxo)2(η1,η1,μ2-carboxylate)2 moieties have
been reported,[17] bent mixed-metal complexes with Cu2M(μ-
alkoxo)2 cores (M = Co,[18] Mn[19]) are limited to a few examples
and, furthermore, no angular mixed-metal trinuclear complex
with a Cu2M(μ-alkoxo)2(η1,η1,μ2-carboxylate)2 core has been re-
ported, based on a CSD analysis.
Figure 4. ORTEP diagram of [CuCo(HL)(OAc)(NO3)2] (3b) with the atomic num-
bering scheme. The thermal ellipsoids are drawn at the 40 % probability level,
and the C–H hydrogen atoms have been omitted for clarity.
protonated HL– ligands and two acetate and two nitrate anions
(see Figure 5 for 4c and Figures S5 and 6 in the Supporting
Information for 4a,b). The structures were refined with a disor-
der model in which the M(OAc)2(NO3) unit and the hydrogen-
–
bonded NO3 anion occupy two sites, each related by Ci sym-
metry with 0.5 occupancy (one set of disordered structures is
illustrated for clarity). Complexes 4a–4c are apparently derived
from the substitution of one of the two nitrate ions in 3a–3c
by the {Cu(OAc)(HL)} fragment. Owing to the presence of two
hydrogen bonds between the O10* atom of the nitrate ion and
the hydroxy O2* and O3 atoms of HL– [O10*···O2* 2.6786(2) Å
(4a), 2.625(1) Å (4b), 2.6635(8) Å (4c); O10*···O3 2.6786(2) Å
(4a), 2.625(1) Å (4b), 2.6635(8) Å (4c)], the three metal ions of
Phosphate-Bridged Cu2M (M = Cu, Co, Mn) and Cu2M2
(M = Co, Zn) Complexes by Using the {Cu(HL)}+ Synthon
CuMCu are arranged in a bent structure [Cu1···M2 3.525(1) Å In the light of the significant influence of carboxylate ligands
(4a), 3.523(2) Å (4b), 3.569(1) Å (4c); Cu1*···M2 3.3085(8) Å (4a), on the trinuclear metal alignment, the phosphate anion
–
3.352(2) Å (4b), 3.455(1) Å (4c); Cu1···Cu1* 6.0710(6) Å (4a), (PhO)2PO2 was introduced in place of the carboxylate ligand.
6.107(2) Å (4b), 6.219(2) Å (4c); Cu1–M2–Cu1* 125.31(3)° (4a), The reaction of 1 with 1 equiv. of (PhO)2PO(OH) in the presence
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of NEt3 in MeOH at room temperature resulted in the formation
of the mononuclear complex [Cu(H2L){(PhO)2PO2}](NO3) (6) in
85 % yield (Scheme 4), with the coordinated nitrate anion of
–
1 replaced by the phosphate anion (PhO)2PO2 (Figure 6 and
Table S12 in the Supporting Information). The copper ion
adopts a distorted trigonal-bipyramidal geometry (τ = 0.52)
with the axial sites occupied by the O3 oxygen atom of the
diphenyl phosphate and the N1 amino nitrogen atom [O3–Cu–
N1 178.79(10)°]. The P1–O4 distance [1.470(2) Å] is marginally
shorter than the P1–O3 distance [1.497(3) Å], with the two P–
OPh distances being considerably longer [1.599(2), 1.607(3) Å].
The O1 hydroxy group is involved in a hydrogen bond with an
oxygen atom of the counter nitrate ion [O1···O7 2.716(3) Å],
and two stronger hydrogen bonds are established between ad-
jacent mononuclear units through the O2 hydroxy group and
the P–O oxygen of O4 [O2···O4* 2.659(3) Å] to form a dimeric
structure (see Figure S7).
Figure 6. ORTEP diagram of the complex cation of 6 with the atomic number-
ing scheme. The thermal ellipsoids are drawn at the 40 % probability level,
and the C–H hydrogen atoms have been omitted for clarity.
c
bridged by acetate ligands. The Cu1···Cu2 distance
[3.304(1) Å] in 7a is significantly shorter than the corresponding
distances in 7b,c [3.6051(4) Å (7b), 3.6544(8) Å (7c)] because of
the absence of axial MeOH ligands at the central Cu2 ion. In
the Cu3 complex 7a, the central Cu2 center adopts a square-
planar geometry ligated by pairs of phosphate and alkoxo oxy-
gen atoms (O1, O1*, O4, and O4*) in a trans configuration [Cu2–
O1 1.941(4) Å, Cu2–O4 1.946(4) Å]. The terminal Cu ions are
pentacoordinated by the N2O2 donors of HL– and one oxygen
atom of the phosphate bridge with τ = 0.33. The protonated
O2 oxygen atom of HL– is involved in a hydrogen bond with an
oxygen atom of the outer nitrate ion [O2···O7 2.704(5) Å]. The
nitrate ion is located far from the axial positions of the Cu2
center, although a weak axial interaction is observed in 5; the
structural difference between 7a and 5 may be ascribed to the
steric bulkiness of the diphenyl phosphate in comparison with
formate. Instead of the nitrate ion in 5, the O2 atom is located
at the axial position of Cu2 with a long distance of Cu2···O2
[2.997(3) Å]. As a result of the weak interaction between the
Cu2 and O2 atoms, the Cu1–O1–Cu2 angle of 116.0(2)° in 7a is
meaningfully smaller than that in 5 [124.56(8)°]. These structural
differences may lead to the Cu1···Cu2 distance of 3.304(1) Å
being appreciably shorter than that of 5 [3.4342(6) Å].
Scheme 4. Preparation of [Cu(HL){(PhO)2PO2}]NO3 (6), [Cu2M(HL)2-
{(PhO)2PO2}2](NO3)2 (7: M = Cu, Mn, Co), and [Cu2M2(HL)2{(PhO)PO3}2(NO3)2]
(8: M = Co, Zn).
The mononuclear complex 6 is also a useful precursor of
Cu2M heterotrinuclear complexes and reacted with 0.5 equiv.
of M(NO3)2 (M = Cu, Co, Mn) in the presence of NEt3 in MeOH
at room temperature to afford the linear homo- and heterome-
tallic trinuclear complexes [Cu3(HL)2{(PhO)2PO2}2](NO3)2 (7a)
and [Cu2M(HL)2{(PhO)2PO2}2(MeOH)2](NO3)2 [M = Co (7b), Mn
(7c)] in yields of 87, 67, and 14 %, respectively (Scheme 4). Com-
plexes 7a–c were also synthesized from the reactions of 4a–c
with 2 equiv. of (PhO)2PO(OH) in MeOH in yields of 76, 84, and
82 %, respectively.
The structures of 7b,c are isomorphous and similar to that
of 7a except for the coordination of two methanol molecules
to the central M2 ion, which results in an octahedral structure
at this site with six normal M2–O bond lengths [2.018(1)–
2.176(2) Å (7b), 2.120(2)–2.220(3) Å (7c); Figure 8]. The terminal
Complexes 7a–c are composed of linear CuMCu metal ions copper ions adopt a distorted square-pyramidal geometry with
(M = Cu, Co, Mn) bridged by two η1,η1-(diphenyl phosphate) τ = 0.42 (7b) and 0.43 (7c). The distances of Cu1–N [2.006(2)–
ligands and two mono-deprotonated HL– ligands (see Figures 7 2.116(2) Å (7b), 1.987(3)–2.113(3) Å (7c)] and Cu1–O [1.942(2)–
and 8 for 7a,b, respectively, and Figure S8 in the Supporting 2.260(2) Å (7b), 1.934(2)–2.269(3) Å (7c)] are comparable to
Information for 7c). The structures clearly indicate that the aux- those in 7a. The two protonated O2 and O7 oxygen atoms are
iliary bridging ligands are crucial to determine the CuMCu trinu- involved in hydrogen bonds with the O9 and O8 atoms of the
clear structures; the linear structures of 7a–c with bridging nitrate ion [O2···O9 2.765(2) Å (7b), 2.771(4) Å (7c); O7···O8
phosphates can be contrasted with the bent structures of 4a– 2.729(2) Å (7b), 2.714(4) Å (7c)]. As a result of the presence of
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gave the Cu2M2 mixed-metal tetranuclear complexes
[Cu2M2(HL)2{(PhO)PO3}2(NO3)2] [M = Co (8a), Zn (8b)] in yields
of 87 and 4 %, respectively (Scheme 4). It should be noted that
a similar reaction of 1 with Cu(OAc)2 did not afford any analo-
gous tetranuclear copper complexes. Complexes 8a,b consist of
Cu2M2 ions supported by two HL– ligands, two phenyl phos-
phates, and two nitrate ions, possessing a crystallographically
imposed inversion center (Figure 9 and Figure S9 in the Sup-
porting Information). The core structures are composed of three
fused macrocyclic rings containing a central [M2O4P2] eight-
membered ring flanked at each side by two outer [CuMO3P]
six-membered rings. The central [M2O4P2] ring is formed by two
tetracoordinate M ions and two PhOPO32– ligands, and the two
outer [CuMO3P] rings are formed by two {Cu(HL)}– synthons,
which are approximately perpendicular to the central ring and
lie in opposite directions, resulting in a staircase-like core struc-
ture. Although a similar core structure has been observed in
[Cu4Cl2(bpy)4(PCh–)2](ClO4)4 [PCh– = 2-(trimethylammonio)ethyl
phosphate],[23] mixed-metal tetranuclear complexes bridged by
phosphate ligands in η1,η1,η1,μ3 mode are limited to a few ex-
amples containing V2M2 (M = Mn, Co, Cu, Zn) ions.[24] Hence, 8
is the first Cu2M2 (M = Co, Zn) mixed-metal structure with
η1,η1,η1,μ3-phosphate bridges. The geometry around the M2
ions is tetrahedral with τ4 values of 0.93 (8a) and 0.93 (8b),[21]
and that around the Cu1 ions is distorted square-pyramidal [τ =
0.18 (8a), 0.18 (8b)] with the hydroxy O2 atom of HL– at the
apical site as observed in 2–5. The protonated O2 atom is in-
volved in an intramolecular hydrogen bond with the phosphate
O4* atom [O2···O4* 2.765(2) Å (8a), 2.771(4) Å (8b)]. The phenyl
Figure 7. ORTEP diagram of 7a with the atomic numbering scheme. The ther-
mal ellipsoids are drawn at the 40 % probability level, and the C–H hydrogen
atoms and phenyl rings have been omitted for clarity. Hydrogen bonds are
shown as dashed lines (O2–O7 and O2*–O7*).
axial MeOH ligands at the M2 center, the Cu1···M2 distances
[3.6051(4) (7b), 3.6544(8) (7c)] are significantly longer than
those in 7a [3.304(1) Å] and, as a result, the Cu1–O1–M2 angles
of 130.59(7)° (7b) and 128.6(1)° (7c) are larger than those in7a
[116.0(2)°]. There are several examples of homometallic tri-
nuclear complexes bridged by phosphate or phosphonate li-
gands,[20] however, mixed-metal trinuclear complexes are lim-
ited to only a few examples with the metal combinations V2M
(M = Mn, Co, Ni, Fe).[20a]
2–
phosphate (PhO)PO3 bridges one Cu ion and two M ions in a
η1,η1,η1,μ3 fashion. The P–O distances [av. 1.516 Å (8a), 1.516 Å
(8b)] for the metal bound oxygens are shorter than the P–OPh
bonds [1.616(2) Å (8a), 1.632(3) Å (8b)], which has been ob-
served in related metal complexes bridged by phosphate or
phosphonate ligands in the η1,η1,η1,μ3 form.[22]
Figure 8. ORTEP diagram of 7b with the atomic numbering scheme. The
thermal ellipsoids are drawn at the 40 % probability level, and the C–H
hydrogen atoms and phenyl rings have been omitted for clarity. Hydrogen
bonds are shown as dashed lines (O2–O9, O7–O8, O2*–O9*, and O7*–O8*).
With the aim of assembling more than three metal ions, the
phosphate mono ester (PhO)PO(OH)2 was utilized instead of
(PhO)2PO(OH). The treatment of 1 with 1 equiv. of M(OAc)2 (M =
Co, Zn) and (PhO)PO(OH)2 in the presence of NEt3 in MeOH
Figure 9. ORTEP diagram of 8a with the atomic numbering scheme. The ther-
mal ellipsoids are drawn at the 40 % probability level, and the C–H hydrogen
atoms and phenyl rings have been omitted for clarity. Hydrogen bonds are
shown as dashed lines (O2–O4* and O4–O2*).
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Figure 10. Systematic preparation of di-, tri-, and tetranuclear homo- and heterometal complexes with Cu2 (2), CuM (3: M = Cu, Co, Zn, Ni), Cu3 (5), bent-
CuMCu (4: M = Cu, Co, Mn), linear-CuMCu (7: M = Cu, Co, Mn), and Cu2M2 (8: M = Co, Zn) cores utilizing the mononuclear {Cu(HL)}– synthon as a metalloligand.
JMN-AL400 spectrometer at 400 and 100 MHz, respectively. IR spec-
tra were recorded as KBr pellets with a Jsaco FT/IR-410 spectrome-
Conclusions
We have synthesized a new N2O2 amino alcohol, N,N-dibenzyl-
N′,N′-bis(2-hydroxyethyl)ethylenediamine (H2L), which acts as a
flexible tetradentate ligand with two intact hydroxy groups and
forms the mononuclear copper complex [Cu(H2L)(NO3)](NO3)
(1). Deprotonation of 1 generated the mononuclear {Cu(HL)}–
synthon, which has proven an effective metalloligand for the
systematic and selective synthesis of novel di-, tri-, and tetranu-
clear homo- and heterometal complexes with various combina-
tions of metal ions to form Cu2 (2), CuM (3: M = Cu, Co, Zn, Ni),
Cu3 (5), bent-Cu2M (4: M = Cu, Co, Mn), linear-Cu2M (7: M =
Cu, Co, Mn), and Cu2M2 (8: M = Co, Zn) cores (Figure 10). The
pentacoordinated copper metalloligand in 2–8 exhibits a vari-
ety of geometrical structures from square-pyramidal to dis-
torted trigonal-bipyramidal with τ values of 0.10–0.68, ascriba-
ble to the flexible nature of the N2O2 ligand. In the various
structures of 2–8, auxiliary bridging ligands, such as acetate,
formate, and mono- and diphenyl phosphate ligands, have a
significant influence on the metal alignments. The present re-
sults will be very useful for developing the systematic expan-
sion of homo- and heterometallic multinuclear complexes by
utilizing so-called “metalloligands”. We are now attempting to
further deprotonate the {Cu(HL)}– synthon to create larger het-
erometal architectures by finely designed techniques.
ter.
N,N-Dibenzyl-N′,N′-bis(2-hydroxyethyl)ethylenediamine (H2L): A
mixture of N,N-dibenzyl-2-chloroethanamine hydrochloride (22.3 g,
75 mmol), 2,2′-iminodiethanolamine (11.8 g, 113 mmol), and
Na2CO3 (22.3 g, 211 mmol) in CH3CN (150 mL) was heated at reflux
for 13 d. The resultant solution was filtered and dried in vacuo. The
residue was extracted with CHCl3 and washed with H2O. The or-
ganic phase was dried with Na2SO4 to afford the product in 93 %
yield (23.9 g). 1H NMR (400 MHz, CDCl3): δ = 7.26–7.13 (m, 5 H),
3.48 (s, 4 H), 3.39 (t, J = 5 Hz, 4 H), 2.57 (t, J = 6 Hz, 2 H), 2.46 (t,
J = 5 Hz, 4 H), 2.43 (t, J = 6 Hz, 4 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 138.0, 129.2, 128.3, 127.1, 59.6, 58.9, 56.9, 52.4,
51.9 ppm.
[Cu(H2L)(NO3)](NO3) (1): A mixture of Cu(NO3)2·3H2O (488 mg,
2.0 mmol) and H2L (658 mg, 2.0 mmol) in MeOH (10 mL) was stirred
for 1 h at room temperature. The resultant solution was layered
with diethyl ether to give blue crystals of 1 (893 mg, 86 %). IR (KBr):
ν = 1497 (s), 1489 (s), 1459 (m), 1384 (s), 1290 (s), 1057 (m), 1016
˜
(m) cm–1. UV/Vis (MeOH): λmax (ε) = 846 nm (113
M
–1 cm–1).
C20H28CuN4O8 (516.01): calcd. C 46.55, H 5.47, N 10.86; found C
46.33, H 5.48, N 10.81.
[Cu2(HL)2](NO3)2 (2): A solution of 1 (515 mg, 1.0 mmol) and NEt3
(156 mg, 1.5 mmol) was stirred at room temperature for 1 h. The
resulting green precipitate was filtered off and crystallized from
MeOH and diethyl ether mixed solvent to afford green crystals of 2
(401 mg, 89 %). Complex 2 was also obtained in 80 % yield by the
reaction of Cu(NO3)2·3H2O (1.0 mmol), H2L (1.0 mmol), and NEt3
Experimental Section
General: All chemicals were purchased and used without further
(1.5 mmol) in MeOH (5 mL). IR (KBr): ν = 1384 (s), 1342 (m), 1299
˜
purification. 1H and 13C NMR spectra were recorded with a JEOL
(m) cm–1
.
UV/Vis (MeOH): λmax (ε)
=
658 (228), 264 nm
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(6.43 × 103
M
–1 cm–1). C40H54Cu2N6O10 (905.99): calcd. C 53.03, H afforded blue crystals of 5·H2O (92.8 mg, 90 %). Complex 5·H2O
6.01, N 9.28; found C 52.63, H 5.77, N 9.20.
was also obtained in 65 % yield by the reaction of Cu(HCO2)2·4H2O
(0.50 mmol), H2L (0.50 mmol), and NEt3 (1.0 mmol) in MeOH (5 mL).
[Cu2(HL)(OAc)(NO3)2] (3a): Cu(OAc)2 (36.4 mg, 0.2 mmol) was
added to a solution of 1 (104 mg, 0.20 mmol) in MeOH (5 mL). The
resulting solution was stirred at room temperature for 1 h. Addition
of diethyl ether (45 mL) afforded blue crystals of 3a (116 mg, 90 %).
IR (KBr): ν = 1608 (s), 1384 (s), 1371 (s), 1291 (s) cm–1. UV/Vis (MeOH):
˜
λmax (ε) = 722 (196), 267 nm (5.98 × 103
M
–1 cm–1). C42H58Co-
Cu3N6O15 (1136.52): calcd. C 46.18, H 5.43, N 7.80; found C 46.87, H
5.05, N 7.72.
IR (KBr): ν = 1558 (s), 1484 (s), 1471 (s), 1384 (s), 1288 (s), 1062 (m),
˜
1016 (m) cm–1. UV/Vis (MeOH): λmax (ε) = 731 (2.30 × 102), 266 nm [Cu(H2L){(PhO)2PO2}](NO3) (6): (PhO)2PO(OH) (63.7 mg,
(6.40 × 103
M
–1 cm–1). C22H30Cu2N4O10 (637.59): calcd. C 41.44, H 0.25 mmol) and NEt3 (27.5 mg, 0.27 mmol) were added to a solution
4.74, N 8.79; found C 41.29, H 4.77, N 8.73.
of 1 (129 mg, 0.25 mmol) in MeOH (5 mL). After stirring at room
temperature for 1.5 h, diethyl ether (45 mL) was added to afford
[CuCo(HL)(OAc)(NO3)2] (3b): A procedure similar to that for 3a,
using 1 (104 mg, 0.20 mmol) and Co(OAc)2·4H2O (49.2 mg,
0.20 mmol), afforded purple crystals of 3b (108 mg, 85 %). IR (KBr):
greenish blue crystals of 6 (149 mg, 85 %). IR (KBr): ν = 1594 (s),
˜
1492 (m), 1454 (m), 1376 (s), 1251 (m), 1205 (m) cm–1
.
C32H38CuN3O9P (703.19): calcd. C 54.66, H 5.45, N 5.98; found C
ν = 1556 (s), 1475 (s), 1446 (m), 1384 (s), 1299 (m), 1276 (m), 1062
˜
54.59, H 5.67, N 6.11.
(m), 1020 (m) cm–1. UV/Vis (MeOH): λmax (ε) = 707 (1.60 × 102),
284 nm (4.10 × 103
M
–1 cm–1). C22H30CoCuN4O10 (632.98): calcd. C
[Cu3(HL)2{(PhO)2PO2}2](NO3)2 (7a)
41.75, H 4.78, N 8.85; found C 41.57, H 4.73, N 8.75.
Method A: (PhO)2PO(OH) (47.2 mg, 0.20 mmol) was added to a
solution of 4a (104 mg, 0.10 mmol) in MeOH (5 mL), and the solu-
[CuZn(HL)(OAc)(NO3)2] (3c): A procedure similar to that for 3a, us-
ing 1 (104 mg, 0.20 mmol) and Zn(OAc)2 (36.5 mg, 0.20 mmol), tion was stirred at room temperature for 2.5 h. The addition of
afforded blue crystals of 3c (110 mg, 85 %). IR (KBr): ν = 1560 (s),
diethyl ether (45 mL) afforded blue crystals of 7a (107 mg, 76 %).
˜
1492 (s), 1473 (m), 1444 (s), 1384 (s), 1301 (s), 1288 (m) cm–1. UV/
Method B: Cu(NO3)2·3H2O (30.1 mg, 0.12 mmol) and NEt3 (26.7 mg,
0.26 mmol) were added to a solution of 6 (175 mg, 0.25 mmol) in
MeOH (5 mL). After stirring the solution at room temperature for
2.5 h, the addition of diethyl ether (45 mL) afforded blue crystals of
7a (160 mg, 87 %).
Vis (MeOH): λmax (ε) = 726 (1.60 × 102), 283 nm (4.50 × 103 –1 cm–1).
M
C22H30CuN4O10Zn (639.43): calcd. C 41.32, H 4.73, N 8.76; found C
41.45, H 4.78, N 8.82.
[CuNi(HL)(OAc)(NO3)2] (3d): A procedure similar to that for 3a, us-
ing 1 (104 mg, 0.20 mmol) and Ni(OAc)2·4H2O (49.5 mg, 0.20 mmol),
Method C: Cu(NO3)2·3H2O (29.6 mg, 0.12 mmol), (PhO)2PO(OH)
(63.9 mg, 0.26 mmol), and NEt3 (51.0 mg, 0.50 mmol) were added
to a solution of 1 (129 mg, 0.25 mmol) in MeOH (5 mL). After stirring
at room temperature for 1.5 h, the addition of diethyl ether (45 mL)
afforded blue crystals of 3d (84.7 mg, 67 %). IR (KBr): ν = 1561 (s),
˜
1507 (s), 1475 (s), 1445 (s), 1384 (s), 1286 (m) cm–1. A small amount
of inorganic impurity prevented satisfactory elemental analysis re-
sults from being obtained. The chemical formula of 3d was deter-
mined by X-ray analysis.
afforded blue crystals of 7a (160 mg, 87 %). IR (KBr): ν = 1589 (m),
˜
1490 (m), 1455 (m), 1392 (s), 1376 (m), 1305 (m), 1201 (s), 1099
[Cu3(HL)2(OAc)2](NO3)2 (4a): Cu(OAc)2 (36.4 mg, 0.2 mmol) and
NEt3 (20.1 mg, 0.20 mmol) were added to a solution of 1 (104 mg,
0.20 mmol) in MeOH (5 mL). The resulting solution was stirred at
room temperature for 4 h. Addition of diethyl ether (45 mL) af-
(m) cm–1. UV/Vis (MeOH): λmax (ε) = 734 (294), 295 (7.50 × 103),
264 nm (9.83 × 103 –1 cm–1). C64H74Cu3N6O18P2 (1467.90): calcd. C
M
52.37, H 5.08, N 5.73; found C 52.76, H 5.23, N 5.79.
[Cu2Co(HL)2{(PhO)2PO2}2(MeOH)2](NO3)2 (7b): By a procedure
similar to that for 7a, 7b was obtained as green crystals in yields of
84 (Method A), 67 (Method B), and 79 % (Method C), respectively.
forded greenish blue crystals of 4a (98.9 mg, 90 %). IR (KBr): ν =
˜
1577 (s), 1425 (s), 1384 (s), 1303 (s), 1070 (s), 1025 (m), 946 (w), 931
(w), 917 (w), 894 (w) cm–1. UV/Vis (MeOH): λmax (ε) = 712 (371),
IR (KBr): ν = 1594 (m), 1488 (s), 1455 (m), 1384 (s), 1311 (m), 1257
˜
266 nm (1.00 × 104
M
–1 cm–1). C44H60Cu3N6O14 (1087.63): calcd. C
(s), 1203 (m), 1101 (m) cm–1. UV/Vis (MeOH): λmax (ε) = 710 (256),
48.59, H 5.56, N 7.73; found C 48.30, H 5.75, N 7.78.
291 (6.81 × 103), 264 nm (8.54 × 103 –1 cm–1). C66H82CoCu2N6O20P2
M
[Cu2Co(HL)2(OAc)2](NO3)2 (4b): A procedure similar to that for 4a,
using 1 (104 mg, 0.20 mmol), Co(OAc)2·4H2O (49.4 mg, 0.20 mmol),
and NEt3 (80.8 mg, 0.80 mmol), afforded purple crystals of 4b
(1527.37): calcd. C 51.90, H 5.41, N 5.50; found C 51.61, H 5.63, N
5.63.
[Cu2Mn(HL)2{(PhO)2PO2}2(MeOH)2](NO3)2 (7c): By a procedure
similar to that for 7a, 7c·5H2O was obtained as green crystals in
yields of 82 (Method A), 14 (Method B), and 20 % (Method C), re-
(86.5 mg, 80 %). IR (KBr): ν = 1577 (s), 1428 (s), 1384 (s), 1303 (s),
˜
1070 (s), 1027 (s), 946 (w), 931 (w), 917 (w), 892 (w) cm–1. UV/Vis
(MeOH): λmax (ε) = 709 (339), 278 nm (1.00 × 104
M
–1 cm–1).
spectively. IR (KBr): ν = 1592 (m), 1490 (s), 1455 (m), 1384 (s), 1311
˜
C44H60CoCu2N6O14 (1083.02): calcd. C 48.80, H 5.58, N 7.76; found
C 48.51, H 5.65, N 7.73.
(s), 1253 (s), 1203 (m), 1103 (m) cm–1. UV/Vis (MeOH): λmax (ε) = 698
(256), 288 (8.55 × 103), 264 nm (1.09 × 103
M
–1 cm–1).
[Cu2Mn(HL)2(OAc)2](NO3)2 (4c): A procedure similar to that for 4a,
using 1 (104 mg, 0.20 mmol), Mn(OAc)2 (34.4 mg, 0.20 mmol), and
NEt3 (19.5 mg, 0.20 mmol), afforded greenish blue crystals of 4c
C66H92Cu2MnN6O25P2 (1617.45): calcd. C 49.19, H 5.75, N 5.21; found
C 49.00, H 5.36, N 5.34.
[Cu2Co2(HL)2{(PhO)PO3}2(NO3)2] (8a): Co(OAc)2·4H2O (49.6 mg,
0.20 mmol), the phenyl monophosphate (PhO)PO(OH)2 (34.9 mg,
0.20 mmol), and NEt3 (20.9 mg, 0.21 mmol) were added to a solu-
tion of 1 (103 mg, 0.20 mmol) in MeOH (5 mL). After stirring the
solution at room temperature for 1.5 h, the addition of diethyl ether
(45 mL) afforded blue crystals of 8a·4H2O (160 mg, 87 %). IR (KBr):
(100 mg, 93 %). IR (KBr): ν = 1577 (s), 1419 (s), 1384 (s), 1307 (m),
˜
1072 (m), 946 (w), 931 (w), 917 (w), 892 (w) cm–1. UV/Vis (MeOH):
λmax (ε)
=
717 (441), 277 nm (1.46 × 104
M
–1 cm–1).
C44H60Cu2MnN6O14 (1079.02): calcd. C 48.98, H 5.60, N 7.79; found
C 48.74, H 5.76, N 7.85.
[Cu3(HL)2(OCOH)2](NO3)2 (5): Cu(OCHO)2·4H2O (44.4 mg,
ν = 1488 (s), 1384 (m), 1292 (m), 1231 (m), 1158 (m), 1109 (m), 1002
˜
0.20 mmol) and NEt3 (40.9 mg, 0.40 mmol) were added to a solution (m) cm–1. UV/Vis (MeOH): λmax (ε) = 266 nm (1.14 × 104
M
–1 cm–1).
of 1 (100 mg, 0.19 mmol) in MeOH (5 mL). After stirring the solution
at room temperature for 2 h, the addition of diethyl ether (45 mL)
C52H72Co2Cu2N6O22P2 (1440.07): calcd. C 43.37, H 5.04, N 5.84;
found C 43.18, H 4.65, N 5.89.
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(Eds.), Catalysis by Di- and Polynuclear Metal Cluster Complexes, Wiley-
VCH, Weinheim, Germany, 1998; c) R. Sessoli, H.-L. Tsai, A. R. Schake, S.
Wang, J. B. Vincent, K. Folting, D. Gatteschi, G. Christou, D. N. Hendrick-
son, J. Am. Chem. Soc. 1993, 115, 1804–1816; d) R. Sessoli, D. Gatteschi,
A. Caneschi, M. A. Novak, Nature 1993, 365, 141–143; e) R. E. P. Winpenny,
J. Chem. Soc., Dalton Trans. 2002, 1–10; f) G. Mezei, C. M. Zaleski, V. L.
Pecorano, Chem. Rev. 2007, 107, 4933–5003.
[Cu2Zn2(HL)2{(PhO)PO3}2(NO3)2] (8b): By a procedure similar to
that for 8a, using 1 (104 mg, 0.20 mmol), Zn(OAc)2 (36.6 mg,
0.20 mmol), (PhO)PO(OH)2 (34.9 mg, 0.20 mmol), and NEt3 (21.5 mg,
0.21 mmol), 8b·H2O was obtained in 4 % yield as pale-blue crystals.
IR (KBr): ν = 1486 (s), 1384 (w), 1297 (m), 1231 (m), 1166 (m),
˜
1110 (m), 1004 (m) cm–1. UV/Vis (MeOH): λmax (ε) = 297 nm (1.50 ×
104
M
–1 cm–1). C52H66Cu2N6O19P2Zn2 (1398.92): calcd. C 44.65, H
[2]
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4.76, N 6.01; found C 44.83, H 4.75, N 5.91.
X-ray Crystallographic Analysis: The crystals 1–8 were quickly
coated with Paratone N oil and mounted on a loop fiber at room
temperature. The crystal and experimental data are summarized in
Tables S1–S6 in the Supporting Information. All data were collected
at low temperature with a Rigaku VariMax Mo/Saturn CCD diffrac-
tometer equipped with graphite-monochromated confocal Mo-Kα
radiation and a rotating-anode X-ray generator RA-Micro7 (50 kV,
24 mA for 8a, 8b) or a Rigaku AFC8R/Mercury CCD diffractometer
equipped with graphite-monochromated Mo-Kα radiation and a ro-
tating-anode X-ray generator (50 kV, 190 mA for 1; 50 kV, 180 mA
for 2, 4a, 5; 50 kV, 100 mA for 7b). A total of 720 (3a, 3b, 4b, 4c, 6,
7a, 7c), 1080 (8a, 8b), 1800 (3c), and 2160 (1, 2, 4a, 5, 7b) oscillation
images, covering a whole sphere of 6° < 2θ < 55° were corrected
by the ω-scan method [–62° < ω < 118° (1, 2, 4a, 5, 7b), –65° < ω
< 115° (3c), –70° < ω < 110° (3a, 3b, 4b, 4c, 7a, 7c, 8a, 8b)] with
Δω of 0.25° (1, 2, 4a, 5, 7b), 0.30° (3c), and 0.5° (3a, 3b, 3d, 4b, 4c,
6, 7a, 7c, 8a, 8b). The crystal-to-detector distance was set at 45 mm
(3a–d, 4b, 4c, 7a, 7c, 8a, 8b), 55 mm (3c), or 60 mm (1, 2, 4a, 5, 6,
7b). The data were processed by using Crystal Clear (version 1.3.5,
Rigaku/MSC)[25] and corrected for Lorentzian-polarization and ab-
sorption effects.[26] The structures of the complexes were solved by
SHELXL-97[27] (2, 4c, 5, 8a) and SIR-92[28] (1, 3a–d, 4a, 4b, 6, 7a–c,
8b) and were refined on F2 with full-matrix least-squares techniques
with SHELXL-97[27] using Crystal Structure 4.1 package.[29] All non-
hydrogen atoms were refined with anisotropic thermal parameters
and the C–H hydrogen atoms were calculated at ideal positions and
refined with riding models. All calculations were carried out on a
Pentium PC using the Crystal Structure 4.1 package.[29]
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CCDC 1452436 (for 1), 1452437 (for 2), 1452438 (for 3a), 1452439
(for 3b), 1452440 (for 3c), 1452441 (for 3d), 1452442 (for 4a),
1452443 (for 4b), 1452444 (for 4c), 1452445 (for 5), 1452446 (for 6),
1452447 (for 7a), 1452448 (for 7b), 1452449 (for 7c), 1452450 (for
8a), and 1452451 (for 8b) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre.
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Supporting Information (see footnote on the first page of this
article): Structural parameters of 1–8 and ORTEP diagrams of 3a,c,d,
4a,b, 6b, 7c, and 8b.
Acknowledgments
This work was supported by a Grant-in-Aid for Scientific Re-
search from the Ministry of Education, Culture, Sports, Science
and Technology (MEXT), Japan. T. N. is grateful to the Tokuyama
Science Foundation, the Kurata Memorial Hitachi Science and
Technology Foundation, and Nara Women's University for a re-
search project grant.
Keywords: Copper · Metalloligands · N,O ligands ·
Heterometallic complexes · Multinuclear complexes
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Received: February 12, 2016
Published Online: April 24, 2016
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim