Article

pubs.acs.org/IC

Synthesis and Characterization of Copper Complexes with CuICuI,

Cu1.5Cu1.5m and CuIICuII Core Structures Supported by a Flexible
Dipyridylamide Ligand
Ethan P. McMoran,† Douglas R. Powell,‡ Felio Perez,§ Gerard T. Rowe,*,∥ and Lei Yang*,†
†
Department of Chemistry, University of Central Arkansas, Conway, Arkansas 72035, United States
‡
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, United States
§
Integrated Microscopy Center, University of Memphis, Memphis, Tennessee 38152, United States
∥
Department of Chemistry and Physics, University of South CarolinaAiken, Aiken, South Carolina 29801, United States
*
S Supporting Information

ABSTRACT: A series of copper complexes supported by a simple

dipyridylamide ligand (H2pcp) were isolated and characterized. Treatment
of H2pcp with NaH and copper(I) salts led to the formation of [Cu2(2pcp)2]
(1a) and {Na[(Cu2(2pcp)2)2]PF6}n (1b). The X-ray crystal structures of both
complexes feature CuICuI cores with close Cu···Cu interactions. Electro-
chemical studies of 1a showed a reversible one-electron oxidation wave in
CH2Cl2. On the basis of the work on 1a, we began studying the mixed-valence
copper species supported by this ligand. The reaction of H2pcp with
Cu(OAc)2 and CuCl in different stoichiometries yielded [Cu2(2pcp)2Cl] (2)
and [Cu3(2pcp)2Cl2] (3). X-ray crystallography and spectroscopic character-
ization suggested delocalized Cu1.5Cu1.5 core structures of both compounds.
These results further inspired us to explore the coordination properties of
H2pcp toward CuII ions. The complexes [HNEt3][Cu2(2pcp)3(ClO4)](ClO4)
(4a), [Cu2(2pcp)3(NO3)] (4b), and [Cu2(2pcp)3(H2O)]BF4 (4c) featuring dinuclear CuIICuII cores were prepared and
characterized by X-ray crystallography and spectroscopic methods. Structural analysis of these complexes implied that the
accommodation of CuICuI, Cu1.5Cu1.5, and CuIICuII is attributed to the structural flexibility of the ligand H2pcp. Complexes 1a,
2, 3, and 4a were examined by X-ray photoelectron spectroscopy, which confirmed the oxidation state assignments.
Computational studies were also performed to provide insight into the electronic structures of these complexes.

■ INTRODUCTION
The presence of mixed-valence copper clusters in biological
systems is of particular interest because of their significant
function in electron-transfer processes and catalysis. For
instance, the two copper centers at the CuA site switch their
oxidation states between CuICuI and delocalized mixed-valence
Cu1.5Cu1.5 to transfer electrons in enzymes such as cytochrome
c oxidase and nitrous oxide reductase.1 In the active sites of
particulate methane monooxygenase (pMMO) and laccase,
localized mixed-valence copper clusters with 1+ and 2+
oxidation states are proposed as intermediates in the catalytic
process based on recent mechanistic and experimental studies.2
In various efforts to understand the mechanisms of these
copper-containing enzymes, small structural and functional
models have been developed and characterized. The reported
examples based on nitrogen-donor ligands such as amine,3
pyrazolate,4 octaazacrytand,5 amidate,6 β-diketiminate,7 and
amidinate8 systems have offered great insight. One major focus
in these modeling studies is to manipulate the ligands to
support copper centers continually when oxidation states
change. Because copper(I) and copper(II) prefer different
geometries and valence intermediates need certain coordination
environments to be stabilized, it still remains challenging to
have a ligand platform that is flexible enough to accommodate
copper ions during the oxidation/reduction process.
As part of our ongoing research on biologically related
copper complexes, we selected pyridylamide ligands as the
supporting scaffolds for copper ions. Our previous work
demonstrated the excellent coordination ability of this system
and the interesting noncovalent interaction induced into the
outer-sphere coordination environment.9 Herein, we report a
simple dipyridylamide ligand that can support CuICuI,
Cu1.5Cu1.5, and CuIICuII dimeric units. Experimental evidence
demonstrated that the tridentate coordination mode and the
coordinative flexibility of this ligand are the major contributing
factors in the stabilization of these clusters. To our best
knowledge, the only ligand system with such a function is
phosphinophenylamido/phosphido.10 The complexes prepared
in this work were fully characterized by X-ray crystallography,
UV−vis, electron paramagnetic resonance (EPR), cyclic
voltammetry, and X-ray photoelectron microscopy (XPS). In
Received: August 17, 2016

© XXXX American Chemical Society A DOI: 10.1021/acs.inorgchem.6b02006

Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
addition, theoretical work was performed to investigate the
electronic structures of these compounds.
■
EXPERIMENTAL SECTION
General Procedures. All reagents were obtained from commercial
sources and used as received unless otherwise noted. The ligand 2-[N-
(2-pyridyl)carbamoyl]pyridine (H2pcp) was synthesized according to
the literature.11 For the synthesis of complexes 1a, 1b, 2, and 3 in a
glovebox, organic solvents were dried over molecular sieves, CaH2 or
sodium/benzophenone, and distilled under vacuum prior to use. 1H
NMR spectra were recorded on a Bruker AVANCE 300 MHz
spectrometer at room temperature. Chemical shifts (δ) were
referenced to the residual solvent signal. UV−vis spectra were
recorded on a Cary 50 spectrometer. X-band EPR spectra were
recorded on a Freiberg Instruments MiniScope MS5000 spectrometer.
The g factors and A coupling constants of EPR spectra were obtained
from simulation using Bruker SimFonia software (version 1.25).
Elemental analyses were carried out by Atlantic Microlabs, Norcross,
GA. Fourier transform infrared (FT-IR) spectra were collected on a
Nicolet Magna 560 FT-IR spectrometer with an attenuated-total-
reflectance attachment. Solution magnetic susceptibility was measured
by using Evans’ method on a Bruker AVANCE 300 MHz spectrometer
at room temperature. Cyclic voltammograms were measured using an
EG&G Princeton Applied Research scanning potentiostat with a three-
electrode cell containing a platinum disk working electrode, a platinum
wire auxiliary electrode, and a Ag/AgCl glass reference electrode. All
measurements were performed in organic solutions containing 1.0 mM
analyte and 0.1 M NBu4BF4 at room temperature with dinitrogen
protection. Recrystallized ferrocene was used as the internal standard.
SQUID data were collected by using a Quantum Design MPSM 3
instrument.
Caution! The perchlorate salt Cu(ClO4)2·6H2O is potentially explosive.
Although we did not experience any problems while conducting the work, it
should be handled with great caution.
For XPS measurements, analysis of the samples was performed
using a Thermo Scientific K-Alpha XPS system equipped with a
monochromatic X-ray source at 1486.6 eV, corresponding to the Al
Kα line. The X-ray power of 75 W at 12 kV was used for all
experiments with a spot size of 400 μm2. The base pressure of the K-
Alpha instrument was at 1.0 × 10−9 mbar. The instrument was
calibrated to give a binding energy of 84.0 eV for Au 4f7/2 and 284.8 eV
for the C 1s line of adventitious (aliphatic) carbon present on the
nonsputtered samples. Photoelectrons were collected from a takeoff
angle of 90° relative to the sample surface. Measurements were done
in the constant analyzer energy mode. The survey spectra were taken
at a pass energy of 200 eV, while the high-resolution (HR) core-level
spectra were taken at a 40 eV pass energy with an energy step size of
0.1 eV and an average of 30 scans. The XPS data acquisition was
performed using the “Avantage v5.932” software provided with the
instrument.
[Cu2(2pcp)2] (1a). CuCl (0.025 g, 0.25 mmol) was added to a
stirring mixture of H2pcp (0.050 g, 0.25 mmol) and NaH (0.006 g,
0.25 mmol) in 2 mL of N,N-dimethylformamide (DMF). The brown
slurry was stirred for 1 h, and 20 mL of Et2O was added to the mixture.
The resulting brown powder was collected and washed with Et2O (5
mL × 3). The powder was extracted with 2 mL of DMF, and vapor
diffusion of diethyl ether (Et2O) into the brown filtrate at room
temperature led to the formation of dark-brown crystals suitable for X-
ray crystallographic characterization (0.033 g, 50% yield). Anal. Calcd
for C22H16N6O2Cu2: C, 50.48; H, 3.08; N, 16.05. Found: C, 50.26; H,
2.95; N, 16.31. FT-IR (cm−1): 1614, 1581, 1553, 1540, 1464, 1425,
1392, 1343, 1287, 1147, 1094, 1046, 1004, 929, 896, 879, 817, 778,
756, 738, 709, 691, 618, 601, 545, 503, 432, 409. 1H NMR (DMF-d7,
298 K): 8.54 (m, 4H), 8.39 (m, 2H), 8.17 (m, 2H), 8.01 (m, 2H), 7.90
(m, 2H), 7.71 (m, 2H), 7.12 (m, 2H). UV−vis [CH2Cl2; λmax, nm (ε,
M−1 cm−1)]: 457 nm (shoulder, 1400).
{Na[(Cu2(2pcp)2)2]PF6}n (1b). [Cu(NCCH3)4]PF6 (0.025 g, 0.25
mmol) was added to a stirring mixture of H2pcp (0.050 g, 0.25 mmol)
and NaH (0.006 g, 0.25 mmol) in 2 mL of CH2Cl2. The brown slurry
B DOI: 10.1021/acs.inorgchem.6b02006
Article
was stirred for 2 h, and the solvent was removed under vacuum. The
resulting brown powder was washed with Et2O (5 mL × 3). The
powder was extracted with 2 mL of acetone, and the turbid solution
was filtered. Vapor diffusion of Et2O into the brown filtrate at room
temperature led to the formation of dark-brown crystals suitable for X-
ray crystallographic characterization (0.031 g, 41% yield). Anal. Calcd
for C44H32N12O4PF6NaCu4: C, 43.50; H, 2.65; N, 13.83. Found: C,
43.22; H, 2.47; N, 13.72. FT-IR (cm−1): 1619, 1586, 1558, 1471, 1432,
1375, 1295, 1161, 1106, 1049, 1008, 830, 776, 751, 739, 698, 634, 617,
558, 514, 449, 426, 407. 1H NMR (DMF-d7, 298 K): 8.53 (m, 4H),
8.38 (m, 2H), 8.13 (m, 2H), 8.01 (m, 2H), 7.90 (m, 2H), 7.70 (m,
2H), 7.11 (m, 2H). UV−vis [CH2Cl2; λmax, nm (ε, M−1 cm−1)]: 457
nm (shoulder, 1370).
[Cu2(2pcp)2Cl] (2). Cu(OAc)2 (0.012 g, 0.065 mmol) was added to
1 mL of a H2pcp solution (0.026 g, 0.13 mol) in 2 mL of DMF, and
the green mixture was stirred for 2 h. CuCl (0.006 g, 0.065 mmol) was
then added to the mixture, and the dark-brownish-green mixture was
stirred for 1 h. A total of 15 mL of Et2O was added to the mixture. The
resulting deep-brown powder was collected and washed with Et2O (5
mL × 3). The powder was extracted with 2 mL of DMF, and the
solution was filtered. Vapor diffusion of Et2O into the dark-brown-
green filtrate at room temperature led to the formation of dark-brown
crystals suitable for X-ray crystallographic characterization (0.020 g,
55% yield). Anal. Calcd for C22H16ClN6O2Cu2: C, 47.27; H, 2.89; N,
15.04. Found: C, 47.11; H, 2.80; N, 14.95. FT-IR (cm−1): 2360, 1678,
1623, 1586, 1469, 1431, 1385, 1355, 1293, 1270, 1153, 1088, 1047,
1016, 938, 881, 821, 781, 765, 711, 692, 675, 651, 618, 555, 542, 504,
464, 455. UV−vis [CH2Cl2; λmax, nm (ε, M−1 cm−1)]: 566 (570), 715
(320). Solution magnetic moment (Evans’ method, 22.0 °C, 7.16 ×
10−3 M, CD2Cl2): 1.86 μB. EPR (9.434 GHz, solution in CH2Cl2, 298
K): g = 2.178 and A = 50 G. EPR (9.434 GHz, frozen solution in
CH2Cl2/tolunene, 77 K): g1 = 2.112, g2 = 2.251, g3 = 2.266, A1 = 15 G,
A2 = 55 G, and A3 = 133 G.
[Cu3(2pcp)2Cl2] (3). Cu(OAc)2 (0.012 g, 0.065 mmol) was added to
1 mL of a H2pcp solution (0.026 g, 0.13 mol) in DMF, and the green
mixture was stirred for 1.5 h. CuCl (0.012 g, 0.13 mmol) was added to
the mixture, and the dark-brownish-green mixture was stirred for 1 h.
A total 15 mL of Et2O was added to the mixture. The resulting deep-
brown powder was collected and washed with Et2O (5 mL × 3). The
powder was extracted with 2 mL of DMF, and the solution was
filtered. Vapor diffusion of Et2O into the dark-brown-green filtrate at
room temperature led to the formation of dark-brown crystals suitable
for X-ray crystallographic characterization (0.024 g, 55% yield). Anal.
Calcd for C22H16Cl2N6O2Cu3: C, 40.16; H, 2.45; N, 12.77. Found: C,
40.28; H, 2.39; N, 12.84. FT-IR (cm−1): 2359, 1623, 1596, 1559, 1471,
1433, 1344, 1294, 1250, 1154, 1090, 1049, 1014, 939, 871, 819, 773,
760, 743, 711, 692, 642, 620, 542, 503, 466, 450, 433. UV−vis
[CH2Cl2; λmax, nm (ε, M−1 cm−1)]: 551 (600), 719 (460). Solution
magnetic moment (Evans’ method, 22.0 °C, 4.72 × 10−3 M, CD2Cl2):
1.69 μB. EPR (9.434 GHz, solution in CH2Cl2, 298 K): g = 2.167 and
A = 47 G. EPR (9.434 GHz, frozen solution in CH2Cl2/toluene, 77
K): g1 = 2.132, g2 = 2.165, g3 = 2.274, A1 = 5 G, A2 = 45 G, and A3 =
103 G.
[HNEt3][Cu2(2pcp)3(ClO4)](ClO4) (4a). A solution of Cu(ClO4)2·
6H2O (0.062 g, 0.17 mmol) in 1 mL of CH3CN was added to a
stirring mixture of H2pcp (0.050 g, 0.25 mmol) and Et3N (0.025g,
0.25 mmol) in 2 mL of CH3CN. The deep-green solution was stirred
for 2 h, and 20 mL of Et2O was added to the mixture. The resulting
green powder was collected and washed with Et2O (5 mL × 3). The
powder was dissolved in 2 mL of CH3CN and filtered. Vapor diffusion
of Et2O into the deep-green solution at room temperature led to the
formation of dark-green crystals suitable for X-ray crystallographic
characterization (0.062 g, 79% yield). Anal. Calcd for
C39H40N10O11Cl2Cu2: C, 45.80; H, 3.94; N, 13.69; Cl, 6.93. Found:
C, 45.40; H, 3.96; N, 13.53; Cl, 6.82. FT-IR (cm−1): 1700, 1685, 1622,
1590, 1559, 1525, 1508, 1474, 1436, 1367, 1298, 1253, 1144, 1113,
1087, 1027, 941, 776, 708, 692, 627. UV−vis [CH3CN; λmax, nm (ε,
M−1 cm−1)]: 661 (230), 751 (240). UV−vis [CH2Cl2; λmax, nm (ε,
M−1 cm−1)]: 632 (260), 761 (250). Solution magnetic moment
(Evans’ method, 22.0 °C, 5.52 × 10−3 M, CD2Cl2): 1.79 μB per
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
copper. EPR (9.434 GHz, solution in CH3CN, 298 K): g = 2.175 and
A = 76 G.
[Cu2(2pcp)3(NO3)] (4b). Complex 4b was synthesized in methanol
(MeOH) by following a procedure similar to that of 4a. Cu(NO3)2·
3H2O was used as the copper(II) salt. Vapor diffusion of Et2O into the
deep-green solution at room temperature led to the formation of dark-
green crystals suitable for X-ray crystallographic characterization
(0.049 g, 48% yield). Anal. Calcd for C33H24N10O6Cu2: C, 50.57; H,
3.09; N, 17.87. Found: C, 50.68; H, 3.06; N, 17.62. FT-IR (cm−1):
1627, 1593, 1562, 1470, 1433, 1348, 1298, 1253, 1156, 1093, 1047,
1025, 939, 854, 815, 762, 708, 691, 652, 620, 534, 506, 465, 435, 409.
UV−vis [CH3CN; λmax, nm (ε, M−1 cm−1)]: 655 (240), 739 (230).
UV−vis [CH2Cl2; λmax, nm (ε, M−1 cm−1)]: 637 (250), 749 (280).
Solution magnetic moment (Evans’ method, 22.0 °C, 5.24 × 10−3 M,
CD2Cl2): 1.78 μB per copper.
[Cu2(2pcp)3(H2O)]BF4 (4c). Complex 4c was synthesized in MeOH
by following a procedure similar to that of 4a. Cu(BF4)2·6H2O was
used as the copper(II) source. Vapor diffusion of Et2O into the deep-
green solution at room temperature led to the formation of dark-green
crystals suitable for X-ray crystallographic characterization (0.069 g,
67% yield). Anal. Calcd for C33H26N9O4BF4Cu2: C, 47.95; H, 3.17; N,
15.25. Found: C, 47.89; H, 3.31; N, 15.42. FT-IR (cm−1): 1621, 1591,
1561, 1469, 1434, 1364, 1300, 1253, 1155, 1055, 1018, 939, 854, 816,
761, 709, 690, 653, 620, 510, 463, 434, 409. UV−vis [CH3CN; λmax,
nm (ε, M−1 cm−1)]: 658 (220), 747 (230). UV−vis [CH2Cl2; λmax, nm
(ε, M−1 cm−1)]: 634 (250), 757 (240). Solution magnetic moment
(Evans’ method, 22.0 °C, 6.26 × 10−3 M, CD2Cl2): 1.75 μB per
copper.
Magnetic Susceptibility of 4a and Magnetic Data Fitting.
The magnetic susceptibility of 4a was measured using a Quantum
Design MPMS SQUID VSM Evercool magnetometer. The sample was
loaded into a polypropylene VSM powder holder. The magnetic
susceptibility (zero-field-cooled) was measured with an applied field of
1000 Oe as a function of the temperature between 2 and 300 K. The
methods of Morrison and zur Loye12 were used to correct for shape
and radial offset effects.
The magnetic susceptibility temperature dependence in 4a was
modeled using the Bleaney−Bowers equation13 for an isolated spin−
spin dimer whose magnetic centers have a coupling constant, J:
2NAg 2μB2 Ceff
χmol of Cu = + + χTIP
−J / k bT
k bT (3 + e ) T−θ
where the second term represents the effective Curie−Weiss law for an
impurity of monomeric material and χTIP is temperature-independent
paramagnetic susceptibility. Minimization of the reliability factor R
[where R = ∑(χmTcalc − χmTobs)2/(χmTobs)2] between temperatures of
2 and 300 K led to the best fit for J = −29 cm−1, and a magnetic field
splitting factor g = 1.93, with R = 2.70 × 10−3.
X-ray Crystallography. X-ray crystallographic data were collected
on crystals with dimensions of 0.56 × 0.39 × 0.37 mm for 1a, 0.39 ×
0.04 × 0.02 mm for 1b, 0.16 × 0.12 × 0.10 mm for 2, 0.08 × 0.06 ×
0.06 mm for 3, 0.50 × 0.15 × 0.04 mm for 4a, 0.52 × 0.40 × 0.18 mm
for 4b, and 0.32 × 0.14 × 0.12 mm for 4c. Data were collected at 100
K using a diffractometer with a Bruker APEX CCD area detector14 and
graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). All seven
structures were solved by direct methods and refined by full-matrix
least-squares methods on F2.15 The crystal parameters, data collection,
and refinement of 1a, 2, 3, and 4a are summarized in Table S1. The
crystal parameters, data collection, and refinement of 1b, 4b, and 4c
are summarized in Table S2. Non-hydrogen atoms were refined with
anisotropic displacement parameters.
Hirshfeld Surface Analysis. In order to investigate the important
intra- and intermolecular interactions occurring within and among the
coordination units, analysis of the Hirshfeld surface was performed by
using CrystalExplorer (version 3.0) software.16 The calculation was
based on the CIF files from the X-ray crystal structures of the metal
complexes.
Computational Chemistry. Starting with X-ray structures, the
optimized geometries of 1a, 2, 3, and 4a were calculated with Gaussian
C DOI: 10.1021/acs.inorgchem.6b02006
Article
09, revision C.01,17 at the M06L18/def2-TZVP19 level of theory.
Dunlap’s density-fitting approximation was employed for all geometry
optimization calculations, with the auxiliary basis sets generated
automatically by the program.20 The identification of each compound’s
structural minimum was confirmed through the absence of imaginary
vibrational modes in an analytical frequency calculation. For the
optimization of 4a structural variants, 4−CH3CN, 4−CH2Cl2, and 4−
CH3CN, implicit solvation was included through the use of COSMO.21
The XPS spectra of 1a, 2, 3, and 4a were interpreted by analysis of
their Cu 2p orbitals using Orca 3.0.3 for Linux.22 These calculations
were carried out at the M06L/def2-TZVP level of theory with the
exception of copper atoms, for which the polarized CoreProp basis set
[CP(PPP)] was utilized.23,24 A higher accuracy integral grid (Lebedev
770 point grid) was also utilized for the copper atoms. For the open-
shell molecules 2, 3, and 4a, the restricted open-wave function was
calculated in order to allow for easier interpretation of orbital energies.
Using Orca 3.0.3, a broken-symmetry calculation was performed on
4a in order to predict the J-coupling value for the dicupric system.
Using the def2-TZVP basis set, it was found that the Coulomb-
attenuated functional cam-B3LYP25 gave the best performance. To
calculate the numerical value of J, the generalized equation26
LS
E(DFT ) − HSE(DFT)
Jab =
HS
⟨S ⟩(DFT) − LS⟨S2⟩(DFT)
2
recommended by Soda et al. was employed.27
Using Orca 3.0.3, gas-phase electronic spectra of 1a, 2, and 3 were
calculated with the double-hybrid RI-B2PLYP functional.28 A mixture
of basis sets (def2-SVP19,29 for carbon, hydrogen, and oxygen; def2-
TZVP for nitrogen, chlorine, and copper) was employed, and the
appropriate correlation auxiliary basis sets (i.e., def2-SVP/c and def2-
TZVP/c) were used in the RI-MP2 portion of the calculations.
Because of the large size of 4a making the B2PLYP calculation
intractable, its electronic spectrum was calculated at the B3LYP/def2-
TZVP level of theory. Selected excited states for these species were
visualized as hole−particle pairs using natural transition orbitals
(NTOs).30 NTO analysis allows for the condensation of a transition
that has many contributions into a small number of hole−particle pairs
that describe the excitation process. All molecular orbital images were
generated using IboView for Windows.31
Results and Discussion. Synthesis and Characterization of 1a
and 1b. The synthesis of 1a is shown in Scheme 1. Treatment of the
Scheme 1. Synthesis of 1a
ligand H2pcp with NaH in DMF yielded a white suspension. The
addition of CuCl turned the suspension to a dark-red solution, which
yielded a deep-brown powder when Et2O was added. Purification of
the powder through recrystallization afforded brown crystals suitable
for X-ray diffraction. Solutions of 1a in organic solvents were air-
sensitive and turned to light-green solutions in a few minutes when
exposed to air.
The X-ray crystal structure of 1a is shown in Figure 1. Also, see
Table 1 for selected bond lengths and angles. Two copper(I) centers
are sandwiched by two deprotonated ligands, which display a μ2-
(κNpy,Namidate;κNpy) coordination mode. For each copper(I) ion, the
coordination environment is fulfilled by two nitrogen donors from one
ligand and the third nitrogen from the second ligand. The two
copper(I) centers have a distance of 2.578 Å that is shorter than the
sum of the copper covalent radii (2.64 Å),32 indicating a weak
interaction. The dimeric unit has a 2-fold rotation axis that crosses the
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Figure 1. X-ray structures of one dimeric unit (left) and two packing units (right) of 1a. Thermal ellipsoids are shown at the 50% level. Most
hydrogen atoms are omitted for clarity. Cu−Cu = 2.578 Å.

Table 1. Selected Bond Lengths (Å) and Angles (deg) of Synthesis and Characterization of 2 and 3. Inspired by the
Complex 1a interesting electrochemical behavior of 1a, we attempted to isolate the
mixed-valence compounds supported by the ligand H2pcp. In the
Cu1−N1A 1.9180(13) N1A−Cu1−N2 169.06(6) absence of base, the treatment of 1 equiv of H2pcp with 0.5 equiv of
Cu1−N3 2.2202(15) N1A−Cu1−N3 109.40(5) Cu(OAc)2, followed by the addition of either 0.5 or 1 equiv of CuCl,
Cu1−N2 1.9309(14) N2−Cu1−N3 81.48(5) led to the isolation of mixed-valence complexes 2 and 3 in DMF
Cu1−Cu1A 2.5780(4) N1A−Cu1−Cu1A 85.62(4) (Scheme 2). Metalation of the amidate group in the ligand H2pcp
N2−Cu1−Cu1A 84.89(4)
N3−Cu1−Cu1A 152.23(4) Scheme 2. Synthesis of 2 and 3

midpoint of the Cu−Cu bond. In the packing structure, two dimeric

units overlap in a face-to-face fashion with a centroid-to-centroid
distance of 3.790 Å (Figure 1, right). In fact, the Hirshfeld surface
analysis based on one dimeric unit does show the distinct blue and red
triangle pairs on the map plotted by the surface index, indicating the
presence of intermolecular π···π interactions between the aromatic
pyridine rings (Figure S1). One interesting structural feature of 1a is
the saddle-shaped conformation in which each ligand twists its two
pyridyl rings with a torsion angle of 27.98°. Initially, we thought the
intermolecular π···π interactions might be a factor for this unique
molecular shape, but the geometry optimization calculations revealed
that the bent shape was also stable in the gas phase. Therefore, the
intermolecular π···π interactions in the crystal structure of 1a are not
necessary to maintain the geometry.
When [Cu(NCCH3)4]·PF6 was used in the synthesis, one-
dimensional polymer 1b with the same dimeric unit as 1a was
isolated through a similar procedure. The X-ray crystal structure shows
that two pairs of dimeric units are connected by one Na+ cation with a
tetrahedral geometry (τ4 = 0.76) that is fulfilled by four oxygen donors
from the CO groups. According to X-ray structure data, the average without a base has been observed in our previous work.9b The
CO bond in 1b is 1.246 Å, which is slightly longer than the CO resulting dark-brownish-green crystals of both complexes are quite
bond (1.234 Å) in 1a. This elongation of the CO bond might be stable in air for months, but the solutions in organic solvents turned to
attributed to the delocalization of electrons through the κ2-amidate green within ∼10 min in air. X-ray crystallography analysis revealed a
group to stabilize Na+ cations. Each Na+ cation is balanced by one dimeric structure in 2 (Figure 2, top) and a trinuclear cluster in 3
PF6− anion, which interacts with one C−H group on the one- (Figure 2, bottom), with selected bond lengths and angles listed in
dimensional chain through an intermolecular hydrogen bond (H···F = Table 2.
∼2.405 Å; Figure S2 and Table S3). In the X-ray crystal structure of 2, a dinuclear core structure similar
The orange-red solution of 1a in CH2Cl2 shows a shoulder around to that of complex 1 was observed. A chloride ligand sits above the
460 nm with a coefficient of 1400 M−1 cm−1, suggesting a charge- dimeric unit and interacts with both copper centers through a distance
transfer property between the deprotonated ligand and the copper(I) of 2.5446(19) Å. Because the two negatively charged amidate ligands
center (Figure S3). The calculated UV−vis spectra (Figure S4) and and one chloride have to be balanced by two copper centers, the total
NTO analysis (Figure S5) further confirmed the primary ligand-to- charge of the two copper ions should be 3+. Interestingly, the Cu1−
metal charge-transfer character of this band. Cyclic voltammetry Cu1A distance in 2 [2.3577(15) Å] is significantly shorter than the
measurement was performed to investigate the oxidation/reduction of Cu−Cu distance in 1 [2.5780(4) Å], indicating a stronger interaction
the copper centers (Figure S6). A reversible wave was observed at E1/2 between the copper centers. These features suggest a delocalized
= 0.095 V vs Ag/AgCl with a scan rate of 100 mV/s. ΔEp (65 mV) is mixed-valence (Cu1.5Cu1.5) property of 2, which is confirmed by EPR,
independent of the scan rates, indicating an electrochemical reversible UV−vis, and XPS evidence (see the following discussion).
property of this wave. The feature suggests the formation of a CuIICuI The X-ray crystal structure of 3 is featured by a trinuclear copper
mixed-valence species upon oxidation of the CuICuI unit. core structure with a trianglar arrangement of the three copper centers.

D DOI: 10.1021/acs.inorgchem.6b02006
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Inorganic Chemistry Article

[Cl1−Cu2−Cl1A = 177.59(5)°] is fulfilled by two chlorides with a

Cu−Cl bond of 2.1176(9) Å. On the basis of the charge balance (two
negatively charged amidate ligands and two chlorides), geometries of
the copper centers, and spectroscopic studies, we assign the Cu1 and
Cu1A dimeric structure as a delocalized mixed-valence (Cu1.5Cu1.5)
unit, while Cu2 as a copper(I) center.
As demonstrated by the spectroscopic evidence and theoretical
calculations (see the following discussion), the [CuCl2]− motif in 3
does not have any significant impact on the electronic structure of the
delocalized mixed-valence dimeric unit. Therefore, the formation of
the trimeric structure is attributed to the electrostatic attraction
between the negatively charged [CuCl2]− unit and positively charged
[Cu2(2pcp)2]+ unit. A close examination of the Hirshfeld surface map
plotted with dnorm for 3 revealed an interesting feature shown in Figure
S7. Two bright-red dots are observed on the surface map of the
[Cu2(2pcp)2]+ unit, indicating weak Cu1···Cl1 and Cu1A···Cl1A
interactions. This feature is confirmed by the large Cu1···Cl1 and
Cu1A···Cl1A distances (2.810 Å) in the X-ray crystal structure.
Apparently, as a result of the weak interactions, the [CuCl2]− unit is
able to anchor on top of the [Cu2(2pcp)2]+ unit and nearly align with
the Cu1−Cu1A bond (torsion angle of Cl1−Cl1A−Cu1A−Cu1 =
12.84°).
UV−vis spectra of complexes 2 and 3 in a CH2Cl2 solution were
collected to understand their electronic structures (Figure S8). Both
compounds show similar bands around 560 and 710 nm, indicating
similar solution structures. Much like the experimental data, the
calculated spectra of the mixed-valence complexes 2 and 3 are similar
to each other (Figure S9). The spectrum of 3 contains all of the major
features seen in that of 2 but is blue-shifted by about 70 nm. This
Figure 2. X-ray structures of complexes 2 (top) and 3 (bottom). similarity in their electronic structures is more evidence for our
Thermal ellipsoids are shown at the 50% level. Hydrogen atoms are description of the [CuCl2]− group being electrostatically bound rather
omitted for clarity. Complex 2: Cu1···Cu1A = 2.358 Å. Complex 3: than participating in a discrete metal−metal bond. NTO analysis of the
Cu1−Cu1A = 2.436 Å; Cu1···Cu2 = 2.867 Å; Cu1A···Cu2 = 2.867 Å. transitions in 2 and 3 support this assignment, as well. The similarity
between the two compounds is illustrated particularly well in the
Table 2. Selected Bond Lengths (Å) and Angles (deg) of representation of the corresponding absorption features of 2 at 583
Complexes 2 and 3 nm and 3 at 507 nm (Figure 3). The nature of these two transitions is
nearly identical, with a majority of the transitions having d → d
Complex 2 character and a smaller contribution that have Cu−Cu σ → σ*
Cu1−N1 1.938(5) N1−Cu1−N2A 151.15(19) character. The only participation that the [CuCl2]− group has in the
Cu1−N2A 1.934(5) N1−Cu1−Cu1A 87.63(13) 507 nm transition of 3 is as part of the ligand orbitals that make up the
Cu1−N3A 2.046(4) N1−Cu1−N3A 107.46(19) hole of the minor σ → σ* component. Despite this participation, the
overall nature of the hole orbital is not fundamentally changed
Cu1−Cl1 2.5446(19) N1−Cu1−Cl1 108.96(14)
compared to that of 2. A similar situation is observed in the lowest-
Cu1−Cu1A 2.3577(15) N2A−Cu1−N3A 83.34(19)
energy transitions of 2 and 3, in which the features have strong
N2A−Cu1−Cu1A 88.26(15) [Cu1.5Cu1.5] → Cl− and [Cu1.5Cu1.5] → [CuCl2]− character,
N2A−Cu1−Cl1 94.23(13) respectively (Figures S10 and S11).
N3A−Cu1−Cu1A 161.62(14) X-band EPR spectra of 2 and 3 were collected in CH2Cl2 solutions
N3A−Cu1−Cl1 101.852(13) (room temperature; Figure 4) and frozen CH2Cl2/toluene solutions
Cu1−Cl1−Cu1A 84.89(4) [1:1 (v/v), 77 K; Figure 5]. The seven-line hyperfine signals observed
Complex 3 at both temperatures suggest that an unpaired electron delocalizes over
two copper nuclei with I = 3/2, confirming the assigned delocalized
Cu1−N1 1.938(5) N1−Cu1−N2A 169.23(10)
mixed-valence Cu1.5Cu1.5 states based on the X-ray crystal structures.
Cu1−N2A 1.934(5) N1−Cu1−Cu1A 85.67(8)
Simulation of experimental spectra gave close g values and A coupling
Cu1−N3A 2.046(4) N1−Cu1−N3A 102.02(10) constants, again suggesting the similar solution structures of the two
Cu1−Cu1A 2.4356(8) N1−Cu1−Cu2 79.59(7) complexes. The solid-state EPR spectra of the two complexes at room
Cu1···Cu2 2.8763(8) N2A−Cu1−N3A 83.35(10) temperature were also collected, but unfortunately no hyperfine
Cu1A···Cu2 2.8763(8) N2A−Cu1−Cu1A 85.51(7) features were observed (Figure S12).
Cu2−Cl1 2.1176(9) N2A−Cu1−Cu2 102.16(7) From the above discussion, we demonstrated the similar structural
Cu2−Cl1A 2.1176(9) N3A−Cu1−Cu1A 153.33(6) and spectroscopic characteristics of 2 and 3. Theoretical work was also
N3A−Cu1−Cu2 141.35(6) performed to better understand the electron structure of the two
Cu1−Cu2−Cu1A 50.27(2) compounds. The identical Mulliken atomic charges and spin densities
of the two copper atoms in 2 (Cu1, charge = 0.1474, spin = 0.3477;
Cl1−Cu2−Cl1A 177.59(5)
Cu1A, charge = 0.1474, spin = 0.3477) and the analogous copper
centers in 3 (Cu1, charge = 0.0339, spin = 0.3218; Cu1A, charge =
In addition to the Cu1−Cu1A dimeric unit similar to that of 2, 0.0339, spin = 0.3218) strongly suggest a delocalized state. The singly
complex 3 has a third copper center Cu2 that is located right above the occupied molecular orbitals (SOMOs) of 2 and 3 derived from UNO
Cu1−Cu1A bond. Cu1 and Cu1A interact with each other through a analysis allow for an intuitive visualization of their unpaired electron
distance of 2.4356(8) Å, which is slightly longer than the Cu1−Cu1A densities, as seen in Figure 6. The UNO visualization highlights the
bond in 2 [2.3577(15) Å] but is still shorter than the Cu1−Cu1A similarity of the frontier orbitals of these two compounds, and the high
bond in 1 [2.5780(4) Å]. For the Cu2 center, the linear geometry symmetry of these orbitals emphasizes the extent of unpaired electron

E DOI: 10.1021/acs.inorgchem.6b02006
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Inorganic Chemistry
Figure 3. NTO comparison between the 583 nm transition of 2 (top)
and the 507 nm transition of 3 (bottom). The percent contribution to
the overall transition is given for each pair of holes (left, blue and
purple) and particles (right, orange and red).
delocalization across the two copper centers, with virtually no unpaired
electron density residing on the formally cuprous Cu2 in 3. Therefore,
the calculated electronic structures of 2 and 3 provide support for the
Figure 4. EPR spectra (black, experimental; red, simulation) of complexes 2 (left) and 3 (right) in CH2Cl2 at room temperature. EPR parameters for
2: g = 2.178; A = 50 G. EPR parameters for 3: g = 2.167; A = 47 G.
F DOI: 10.1021/acs.inorgchem.6b02006
Article
assignment of these compounds as delocalized mixed-valence
Cu1.5Cu1.5 species with either a bridging chloride or a [CuCl2]− group.
Cyclic voltammetry characterization of 2 and 3 was performed in
CH2Cl2 solutions with dinitrogen protection. The two complexes
showed reversible oxidative waves around E1/2 = −0.11 V (complex 2;
Figure S13, left) and E1/2 = −0.095 V (complex 3; Figure S14, left),
both of which are assigned as the CuICuI/CuIICuI couple of the
dimeric unit. ΔEp (264 mV in 2 and 256 mV in 3) of the waves
showed no significant change with different scan rates. In comparison
to the CuICuI/CuIICuI wave of 1a (E1/2 = 0.09 V), the lower oxidation
potentials of 2 and 3 might result from the presence of an electron-
donating chloride ligand.
In addition to the CuICuI/CuIICuI couple, 2 showed an irreversible
oxidation wave at E = 0.79 V (Figure S13, right). 3 also showed a
reversible oxidation wave at E1/2 = 0.82 V (Figure S14, right), which
gradually became irreversible at low scan rates. Both waves are
assigned as the CuIICuII state formed from the oxidation of CuIICuI
core structures. Because of coordination of the chloride ligand to the
copper center in 2, it is possible that structural reorganization during
oxidation of the copper ions leads to the formation of geometries that
favor the copper(II) state, therefore causing irreversibility. However,
for 3, dissociation of the linear [CuCl2]− unit exposes the mixed-
valence dimeric unit to oxidation with less influence from Cl−, thus
leading to the slightly higher oxidation potential and its reversibility
between the CuIICuI and CuIICuII states at high scan rates. No
oxidation behavior was observed for the Cu2 center in 3 because of the
fact that a copper center with a linear geometry is usually resistant
toward oxidation.33
Synthesis and Characterization of 4a−4c. On the basis of the
coordination structures and electrochemical behavior of complexes 2
and 3, we envisioned that the ligand H2pcp would also be an excellent
platform to support fully oxidized copper(II) clusters. In fact, in our
previous work based on the ligand H2pcp, we have demonstrated the
interesting coordination properties of the amidate group through
amide proton migration or metalation in the absence of a base.9b In
the resulting mononuclear and dinuclear copper(II) complexes, strong
coordinating anions, such as Cl− and OAc−, were required as terminal
ligands to support the copper(II) center(s). In an effort to minimize
the influence from anions, we employed copper(II) salts with weak or
noncoordinating anions such as ClO4−, NO3−, and BF4−. Scheme 3
illustrates the synthesis and structure of the dinuclear copper(II)
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Figure 5. EPR spectra (black, experimental; red, simulation) of complexes 2 (left) and 3 (right) in frozen 1:1 CH2Cl2/toluene (v/v) at 77 K. EPR
parameters for 2: g1 = 2.112; g2 = 2.251; g3 = 2.266; A1 = 15 G; A2 = 55 G; A3 = 133 G. EPR parameters for 3: g1 = 2.132; g2 = 2.165; g3 = 2.274; A1 =
5 G; A2 = 45 G; A3 = 103 G.

Figure 6. UNO-SOMO images of complexes 2 (A) and 3 (B).

Scheme 3. Synthesis of 4a

Figure 7. X-ray structures of 4a. Thermal ellipsoids are shown at the

50% level. Cu1···Cu2 = 2.9896(14) Å.

fashion, leading to different coordination geometries of the copper

complex 4a. Et3N was applied first to deprotonate the amide group in
the ligand H2pcp, followed by the addition of 2/3 equiv of Cu(ClO4)2·
6H2O in CH3CN. Similar reactions with different stoichiometry ratios
(1:1 ratio of ligand to metal) or in different solvents (MeOH and
acetone) afforded the same compound, suggesting the excellent
stability of 4a. X-ray crystallography revealed a novel dimeric structure
supported by three deprotonated ligands. Because of the slight
disorder of the copper(II) centers in 4a, Cu(NO3)2·3H2O and
Cu(BF4)2·6H2O were applied in the synthesis to obtain better
structures. As a result, structural analogues of 4a−4c were isolated and
purified. All three complexes were very stable in both solid and
solution states, and no changes were observed when stored in air for
months.
Figure 7 depicts the X-ray crystal structure of 4a, and Table 3 shows
the selected bond lengths and angles. Two copper(II) centers are
supported by three bridging amidate ligands in an unsymmetrical
sites. Cu1 is chelated by one amidate nitrogen and one pyridyl
nitrogen from the ligand highlighted in blue, and the coordination
environment is fulfilled by two pyridyl nitrogens from two other
ligands (red and green) and one weakly coordinated ClO4− anion. The
τ5 value of Cu1 is 0.18, suggesting a distorted square-pyramidal
geometry with an elongated axis [Cu1−O1E = 2.623(4) Å; dashed line
in Figure 7], while for the Cu2 center, two deprotonated ligands (red
and green) chelate it through amidate and pyridyl nitrogen donors,
and the fifth position is occupied by the pyridyl nitrogen from the
third ligand (blue). The τ5 value of 0.56 indicates that the geometry of
Cu2 is a structural intermediate between the standard square-
pyramidal and trigonal-bipyramidal geometries. The Cu1···Cu2
distance of 4a (2.990 Å) is much larger than those in the CuICuI
(∼2.578 Å in 1a) and Cu1.5Cu1.5 (∼2.358 Å in 2) dimers, suggesting
no direct interactions between the copper centers.
Complexes 4b and 4c have dimeric core structures nearly identical
with that of 4a but with different axial ligands on the Cu1 center
(Figure S15). The NO3− anion coordinates to the Cu1 atom in 4b

G DOI: 10.1021/acs.inorgchem.6b02006
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Inorganic Chemistry Article

Table 3. Selected Bond Lengths (Å) and Angles (deg) of Cyclic voltammetry measurement of 4a in CH2Cl2 showed a
Complex 4a reversible wave at E1/2 = −0.13 V in both scan directions, which is
attributed to a CuICuII/CuIICuII couple (Figures S20, left, and S21).
Cu1−N1A 2.024(4) N1A−Cu1−N1B 97.11(16) Consideration of the copper center geometries in 4a suggests that Cu1
Cu1−N1B 1.985(4) N1A−Cu1−N2C 95.19(17) is the oxidation/reduction site because its square-pyramidal geometry
Cu1−N2C 1.964(4) N1A−Cu1−N3C 164.7(2) with a weakly coordinated ClO4− anion requires less structural
Cu1−N3C 2.023(4) N1B−Cu1−N2C 154.0(2) rearrangement during reduction and oxidation. Further scans showed
Cu1−O1E 2.623(4) N1B−Cu1−N3C 92.20(17) the independence of ΔE (200 mV) toward scan rates (Figure S20,
right), indicating the electrochemical reversibility of this wave. One
N2C−Cu1−N3C 81.19(17)
irreversible peak was also observed at −0.83 V, which might be the
Cu2−N2A 1.950(4) N1C−Cu2−N2A 94.11(17) reduction of the Cu2 center with the distorted trigonal-bipyramidal
Cu2−N1C 2.059(4) N1C−Cu2−N2B 130.69(18) geometry. The structure rearrangement required for the accommoda-
Cu2−N2B 2.133(5) N1C−Cu2−N3A 139.8(2) tion of copper(I) during the reduction of copper(II) may cause the
Cu2−N3A 2.120(4) N1C−Cu2−N3B 92.08(17) irreversibility.
Cu2−N3B 1.987(4) N2A−Cu2−N2B 98.2(2) In an effort to directly compare the oxidation states of the copper
N2A−Cu2−N3A 80.90(17) centers in complexes 1a, 2, 3, and 4a, XPS measurements were
Cu1···Cu2 2.9896(14) N2A−Cu2−N3B 173.17(18) preformed. The binding energy of Cu 2p electrons obtained from this
N2B−Cu2−N3A 89.39(17) technique can reveal important information regarding copper
N2B−Cu2−N3B 79.82(18)
oxidation states.34 As shown in Table 4 and Figure 8, a solid sample
N3A−Cu2−N3B 92.50(18)
Table 4. Cu 2p3/2 and Cu 2p1/2 Binding Energies from XPS
Measurements
through a long Cu1−O1D distance of 2.494(4) Å, while the water
(H2O) molecule coordinates to the Cu1 atom in 4c with a Cu1−O1S binding energy (eV)
bond of 2.333(5) Å due to the noncoordinating property of the BF4− Cu 2p3/2 Cu 2p1/2
anion. A comparison of the three structures revealed some interesting
1a 931.9 ± 0.06 951.7 ± 0.06
features: (a) In the solid state, the Cu1 center is stabilized by weak
coordination from the fifth ligand, either an anion from the copper(II) 2 932.8 ± 0.02 952.5 ± 0.02
salt or a H2O molecule from the solvent. (b) The increasing size of the 3 932.6 ± 0.03 952.4 ± 0.03
weakly coordinated axial ligands H2O (28.33 Å3) < NO3− (51.62 Å3) < 4a 936.3 ± 0.46 956.5 ± 0.29
ClO4− (66.76 Å3)16 is reflected by the increasing Cu1−O bond
distances Cu1−O1S [H2O, 2.333(5) Å] < Cu1−O1D [NO3−,
2.494(4) Å] < Cu1−O1E [ClO4−, 2.623(4) Å]. (c) No disorder was
observed on copper(II) sites when noncoordinating the BF4− anion
was used. The last feature provided detailed information about the
structure with better accuracy. For instance, the τ5 values of Cu1 and
Cu2 in 4c are 0.35 and 0.57, respectively, confirming the geometry
assignments based on the X-ray data of 4a. The Cu1···Cu2 distances of
4a [2.9896(14) Å] and 4c [2.9778(11) Å] are also comparable. The
selected bond lengths and angles of 4b and 4c are presented in Table
S4.
Electronic absorption spectra of 4a were collected in CH3CN and
CH2Cl2 (Figure S16). Two d−d bands were observed at 640 and 756
nm in both solvents. In computational analysis of the UV−vis
properties of 4a, we examined the role of the axial ClO4− ligand on
Cu1 (Figure S17) with solvent effects. The calculated UV−vis spectra
without ClO4− showed two peaks at 650 and 771 nm in both solvents
(Figure S17, right), which are comparable to the experimental results.
In contrast, the coordination of ClO4− on Cu1 significantly shifted the
bands (Figure S17, left) relative to the experimental spectra.
Therefore, we conclude that ClO4− dissociates from the Cu1 center
when dissolved in weak or noncoordinative solvents, and the influence
of these solvent molecules on the structure is negligible.
The X-band EPR spectrum of 4a in a CH3CN solution was
collected at room temperature (Figure S18). The four-line hyperfine Figure 8. XPS spectra of complexes 1a, 2, 3, and 4a recorded in the
pattern indicated that the unpaired electron interacts with only one Cu 2p region.
copper(II) center. This observation was evidenced by the magnetic
studies of the complex. Effective magnetic moment (μeff) measurement
of 4a in CD2Cl2 at room temperature by using Evans’ method gave a of 1a exhibits a Cu 2p3/2 peak at 931.9 ± 0.06 eV that is comparable
value of 1.79 μB for each copper(II), suggesting localization of the with that of CuICl (2p3/2 = 932.2 eV).35 In contrast, 4a shows a Cu
single electron on each copper center. SQUID measurement from 2 to 2p3/2 peak at 936.3 ± 0.46 eV and a strong satellite peak, which is a
300 K was also performed (Figure S19). The χm data fitting gave a J typical feature for copper(II) compounds.34−36 The most interesting
value of −29 cm−1, which means the two copper centers interact with feature is the Cu 2p3/2 peaks at 932.8 ± 0.02 and 932.6 ± 0.03 eV
each other with a weak antiferromagnetic coupling. The μeff value at exhibited by 2 and 3, which locate between the Cu 2p3/2 peaks of 1a
room temperature obtained from SQUID (1.78 μB per copper) also and 4. This observation clearly suggests intermediate oxidation states
matches well with the data obtained from Evan’s method (1.79 μB per of 2 and 3 between I and II. This Cu 2p3/2 binding energy trend (1a <
copper), indicating conservation of the dimeric structure of 4a in a 2 ≈ 3 < 4a) was also observed from the Cu 2p1/2 peaks in the 951.7−
CH2Cl2 solution. These data match well with the results of a broken- 956.5 eV range. This is consistent with oxidation state assignment for
symmetry CAM-B3LYP calculation on the dimeric structure of 4a, the four complexes based on X-ray crystallography and spectroscopic
which predicts a J value of −30 cm−1. evidence.

H DOI: 10.1021/acs.inorgchem.6b02006
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Inorganic Chemistry
By analysis of the calculated Cu 2p orbital energies of complexes 1a,
2, 3, and 4a, XPS of these compounds can also be rationalized. To
increase the accuracy of these calculations, the integral grid was
increased significantly and the Orca core-property basis set [CP(PPP)]
was used for the copper centers. To aid in the interpretation of the
results, a restricted open-wave function was calculated for the open-
shell molecules 2, 3, and 4a. The resulting Cu 2p orbital energies for
each of these compounds are shown in Scheme 4. The trend observed
Scheme 4. Calculated Cu 2p Orbital Energies for
Compounds 1a, 2, 3, and 4a
here is consistent with the experimental XPS data, in both the binding
energies and the widths of the peaks. In 3, there are two distinct
copper environments and binding energies corresponding to the
mixed-valence Cu1.5Cu1.5 and cuprous [CuCl2]− groups. These two Cu
2p energy regimes in 3 match well with the individual environments in
1a and 2. The expected double peak is not observed in XPS of 3,
which might be due to convolution of the copper(I) signal with the
mixed-valence signal because the latter is rather broad. Another XPS
feature that is explained by these calculations is the broadness of the
peak from 4a. Unlike the other compounds, 4a is a polar and less
symmetric molecule, both of which give rise to greater directional
anisotropy for the Cu 2p orbitals. This results in a predicted breadth of
energy of 0.21 eV, over 20 times greater than that for the CuI species
(0.01 eV).
Given the X-ray crystal structure data of all four complexes, it would
certainly be interesting to inspect the coordinative flexibility exhibited
by the amidate ligand 2pcp− that accommodates the copper centers
with different oxidation states. Figure 9 shows the graphical overlay of
the dimeric copper core structures of 1a (green), 2 (blue), and 3
(red), in which the pyridyl rings with the N1 donors from the three
Figure 9. Dimeric copper core structure overlay of complexes 1a
(green), 2 (blue), and 3 (red) based on the pyridyl ring with the N1
donor. The Cl1 donor of 2 and the [CuCl2]− unit in 3 are omitted for
clarity. Complex 4 is not shown because of the presence of three
amidate ligands.
I DOI: 10.1021/acs.inorgchem.6b02006
Article
complexes are superposed to compare the conformations for the rest
of the structures. Complex 4 is not shown because of the presence of
three amidate ligands. Foremost of the observed features is the
different Cu−Cu distances in complexes 1a (∼2.578 Å), 2 (∼2.436 Å),
3 (∼2.358 Å), and 4a (∼2.990 Å) supported by the ligands with the
same μ2-(κNpy,Namidate;κNpy) coordination mode. Additionally, as
shown in Figure 9, the top ligands of complexes 1a, 2, and 3 have
comparable conformations, but the bottom ligands showed very
different spatial orientations. As a result, the average Cu−N bond
length (∼2.020 Å) of 1a is longer than the ∼1.973 Å length observed
in 2 and 3. Another distinctive conformation feature is the torsion
angle of the two pyridyl rings within an amidate ligand. It varies from
27.98° in 1 to 26.48° in 2 to 12.37° in 3. For 4, the three ligands adapt
even larger dipyridyl torsion angles (39.23−43.91°) to fulfill the
distorted square-pyramidal and trigonal-bipyramidal geometries of the
two copper(II) centers. Therefore, our analysis based on these features
revealed that the flexible coordination behavior exhibited by the ligand
2pcp− should be attributed to the rotation of the pyridyl rings and
bending of the amidate group.
■ CONCLUSION
With X-ray crystallography and spectroscopic characterization,
we have demonstrated the ability of the dipyridylamide ligand
H2pcp to support copper complexes with different oxidation
states. The CuICuI core in complex 1a is stabilized by two
deprotonated H2pcp ligands with a μ2-(κNpy,Namidate;κNpy)
coordination mode. Electrochemical studies showed a rever-
sible oxidation/reduction wave assigned as a CuICuI/CuIICuI
couple, which inspired us to establish the synthetic procedures
for valence intermediates. The resulting dinuclear and trinuclear
copper complexes 2 and 3 with mixed-valence core structures
were characterized by X-ray crystallography and spectroscopic
methods. EPR of both complexes at room temperature and 77
K showed characteristic seven-line hyperfine signals, suggesting
delocalized Cu1.5Cu1.5 mixed-valence states of the complexes.
These results prompted us to further isolate complex 4
featuring a dimeric CuIICuII core structure supported by three
amidate ligands. In contrast to the close Cu−Cu interactions in
1a, 2, and 3, spectroscopic and magnetic studies of 4 have
demonstrated a weak antiferromagnetic interaction between the
two copper(II) centers because of the large Cu···Cu distance.
XPS measurements of all four complexes have clearly shown
the increasing trend of Cu 2p electron binding energy with the
increasing oxidation states (1a < 2 ≈ 3 < 4a). These results
served as clear evidence about the intermediate valence of 2
and 3 between copper(I) and copper(II). The unrestricted
NTO analysis revealed the similar electronic structures of
mixed-valence complexes 2 and 3, which are responsible for the
similar spectroscopic properties of the two compounds. In
addition, the calculated Cu 2p orbital energies rationalized the
XPS features observed for complexes 1a, 2, 3, and 4a.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.6b02006.
Spectroscopic data and cyclic voltammetry (PDF)
X-ray crystallographic data in CIF format (CIF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: gerardr@usca.edu.
*E-mail: lyang@uca.edu. Fax: +1-(501)-450-3623.
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the start-up fund provided by the
College of Natural Sciences and Mathematics and University
Research Council from the University of Central Arkansas,
Arkansas Science & Technology Authority, from the State of
Arkansas. We thanks INBRE of Arkansas for the purchase of
the EPR instrument. We also thank Magnus Pauly for preparing
samples of complex 1a.
■ REFERENCES
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K DOI: 10.1021/acs.inorgchem.6b02006
Inorg. Chem. XXXX, XXX, XXX−XXX