Synthesis, spectral characterization, redox properties of [Cu(4-ampc)2]BPh4 and [Cu(4-ampc)(PPh3)2]BPh4: Crystal structure of [Cu(4-ampc)2]BPh4

Article abstract of DOI:10.1080/15533170802293261

The ligand, morpholin-4-yl-pyridin-2-ylmethylene-amine 4-ampc, and its corresponding copper(I) complexes, [Cu(4-ampc)2]BPh4 1, and [Cu(4-ampc)(PPh3)2] BPh4 2, have been synthesized and characterized by CHN analyses, 1H-NMR, IR, and UV-Vis spectroscopies. The crystal and molecular structures of [Cu(4-ampc)2]BPh4 1 were determined by X-ray crystallography from a single-crystal. The coordination polyhedron about copper(I) is best described as a distorted tetrahedron. Quasireversible and irriversible redox behaviors were observed for 1 and 2, respectively.

Full text of DOI:10.1080/15533170802293261

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Synthesis, Spectral Characterization, Redox
Properties of [Cu(4-ampc)2]BPh4 and [Cu(4-ampc)
(PPh3)2]BPh4: Crystal Structure of [Cu(4-ampc)2]BPh4
Saeed Dehghanpour a & Frank Rominger b
a Department of Chemistry , Alzahra University, Vanak , Tehran, Iran
b Institute of Organic Chemistry, University of Heidelberg , Heidelberg, Germany
Published online: 05 Sep 2008.
To cite this article: Saeed Dehghanpour & Frank Rominger (2008) Synthesis, Spectral Characterization, Redox Properties
of [Cu(4-ampc)2]BPh4 and [Cu(4-ampc)(PPh3)2]BPh4: Crystal Structure of [Cu(4-ampc)2]BPh4 , Synthesis and Reactivity in
Inorganic, Metal-Organic, and Nano-Metal Chemistry, 38:7, 598-603
To link to this article: http://dx.doi.org/10.1080/15533170802293261
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 38:598–603, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533170802293261
Synthesis, Spectral Characterization, Redox Properties
of [Cu(4-ampc)2]BPh4 and [Cu(4-ampc)(PPh3)2]BPh4:
Crystal Structure of [Cu(4-ampc)2]BPh4
Saeed Dehghanpour1 and Frank Rominger2
1Department of Chemistry, Alzahra University, Vanak, Tehran, Iran
2Institute of Organic Chemistry, University of Heidelberg, Heidelberg, Germany
yl-pyridin-2-ylmethylene-amine and their copper(I) complexes
(Figure 1). The spectral properties, redox chemistry, and struc-
ture of these complexes are also discussed.
The ligand, morpholin-4-yl-pyridin-2-ylmethylene-amine 4-
ampc, and its corresponding copper(I) complexes, [Cu(4-
ampc)2]BPh4 1, and [Cu(4-ampc)(PPh3)2]BPh412, have been syn-
thesized and characterized by CHN analyses, H-NMR, IR, and
UV-Vis spectroscopies. The crystal and molecular structures of
[Cu(4-ampc)2]BPh4 1 were determined by X-ray crystallography
from a single-crystal. The coordination polyhedron about copper(I)
is best described as a distorted tetrahedron. Quasireversible and
irriversible redox behaviors were observed for 1 and 2, respectively.
EXPERIMENTAL
All chemicals used were reagent grade and used as re-
ceived. Solvents used for the reactions were purified by lit-
erature methods.[24] [Cu(MeCN)4]BPh4 was freshly prepared
in acetonitrile according to the procedure,[25] washed with cold
acetonitrile, and dried under vacuum. Elemental analyses were
performed by means of a Heraeus CHN-O-RAPID elemental an-
alyzer (Alzahra University). IR spectra were recorded on a Shi-
madzu IR-460 instrument (Alzahra University). Electronic ab-
sorption spectra were recorded on a JASCOV-570 Spectropho-
Keywords copper(I) complexes, diimine ligand, 4-aminomorpho-
line, crystal structure, cyclic voltammogram
INTRODUCTION
The monovalent copper (d10) chemistry has drawn special
attention because of its instability, unusual structural features,
utility in solar energy and supramolecular devices, catalytic ac-
tivity in photo-redox reactions, and the biological relevance
of high potential copper complexes.[1−10] Proper combination
of the steric crowding and π-acidity in a well-designed lig-
and are the most important prerequisites for high stability of
copper(I) complexes.[11,12] Iminopyridine ligands to stabilize
low valent metal-redox states seem to be a good candidate for
such studies and these ligands are used for synthesis of Cu(I),
Re(I), and Ru(II) complexes in such studies.[13−16] However,
the substituent on the iminopyridine ligands may modify the
π-acidity and regulate the physical and chemical properties of
the complexes.[17−21]
1
tometer; λmax (log ε) in nm. H-NMR spectra were measured
with Bruker ACP-200 spectrometer at 200 MHz; chemical shifts
are reported in ppm relative to an internal standard of Me4Si
(Shahid Behesti University). Electrochemical data were ob-
tained by cyclic voltammetry (CV) with a three-electrode cell
consisting of an Ag/AgCl reference electrode, a Pt wire counter
electrode, and the Pt as a working electrode. A Metrohm mul-
tipurpose instrument model 693 VA processor with 694A Va
stand was used. CV measurements were performed in CH2Cl2
with 50 mM Bu4NClO4 (TBAP) as supporting electrolyte. In
all electrochemical experiments, the solutions were purged with
Ar gas for at least 5 min.
Crystal Structure Determination
In continuation of our work on the preparation of copper(I)
diimine complexes with low-lying MLCT transitions,[13,22,23]
we report the synthesis and characterization of morpholin-4-
Diffraction data for 1 were collected on a Bruker Smart AXS
CCD diffractometer using graphite-monochromated MoKα ra-
˚
diation (λ = 0.71073 A) at Institute of Organic Chemistry in
Heidelberg University. An empirical absorption correction was
applied using SADABS[26] based on the Laue symmetry of
the reciprocal space. Structure was solved by direct methods
and refined against F2 with a full-matrix least-squares algo-
rithm using the SHELXTL-PLUS (5.10) software package.[27]
Hydrogen atoms were treated using appropriate riding mod-
els. Crystallographic data (excluding structure factors) for the
Received 4 February 2008; accepted 8 June 2008.
S.D. acknowledges the Alzahra University Research Council for
partial support of this work.
Address correspondence to Saeed Dehghanpour, Department of
Chemistry, Alzahra University, Tehran, Iran. E-mail: dehganpour
farasha@yahoo.com
598

SPECTRAL CHARACTERIZATION
599
of BPh4), 7.72 (t, 2H, JH2,1 = 7.9, JH2,3 = 11.5 Hz, H2), 8.16
(d, 2H, JH1,2 = 7.9 Hz, H1), 8.30 (s, 2H, H5). Anal. Calcd. for
C44H46BCuN6O2 (%): C, 69.06; H, 6.06; N, 10.98. Found: C,
69.08; H, 6.07; N, 10.97.
H3
H4
H5
N
H
H2
2
N
N
N
O
N
N
O
BPh4
H1
O
BPh4
Cu
Cu
Ph3P
N
PPh3
N N
Synthesis of (Morpholin-4-yl-Pyridin-2-Ylmethylene-
Amine)bis(Triphenylphosphine)Copper(I)
Tetraphenylborate, [Cu(4-ampc)(PPh3)2]BPh4, 2
FIG. 1. Chemical formula of Cu(I) complexes 1 and 2.
To a 3-mL acetonitrile solution of [Cu(CH3CN)4]BPh4
(54.8 mg, 0.1 mmol), 2 equivalent of Ph3P (52.2 mg, 0.2 mmol)
were added, and the solution was stirred for 15 min. The sol-
vent was evaporated under vacuum at room temperature. The
dry product [Cu(CH3CN)2(PPh3)2]BPh4 was added to a stir-
ring solution of 19.1 mg (0.1 mmol) morpholin-4-yl-pyridin-2-
ylmethylene-amine, 4-ampc, in 3 mL acetonitrile. The solution
rapidly turned yellow and it was stirred for 20 min at room tem-
perature. The reaction medium was concentrated under vacuum,
until the first crystals appeared in the liquid phase. Bright yellow
crystals were obtained by diffusion of diethylether vapor into the
concentrated solution. Yield: 80 mg (91%). IR data (KBr pellets,
cm−1): 1580 (C N). 1H NMR (CDCl3; δ): δ = 3.13–3.29 (m,
4H, CH2 N CH2 ), 3.59–3.65 (m, 4H, CH2 O CH2 ),
structure 1 reported in this article have been deposited with the
Cambridge Crystallographic Data Center, CCDC No. 675854.
A copy of the data can be obtained free of charge on appli-
cation to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(fax: +44 1223 336033; E-mail: deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk).
Synthesis of Morpholin-4-yl-Pyridin-2-Ylmethylene-
Amine, 4-ampc
Although, this ligand synthesized before,[28] here we report
a simple method for synthesis of the ligand. To a solution of
pyridine-2-carbaldehyde (107 mg, 1 mmol) in 5 mL diethylether
was added a solution of 4-aminomorpholine (102 mg, 1 mmol) in
5 m: diethylether and stirred for 15 min. The ligand, morpholin-
4-yl-pyridin-2-ylmethylene-amine, 4-ampc, was obtained as a
yellow microcrystalline precipitate. It was then filtered off,
washed with cold diethylether, and dried in air. Yield: 80%.
IR data (KBr pellets, cm−1): 1621 (C N). 1H-NMR (500 MHz,
CDCl3): 1H-NMR (CDCl3, ppm): δ = δ = 3.11–3.21 (m, 4H,
CH2 N CH2 ), 3.63–3.69 (m, 4H, CH2 O CH2 ), 7.18
6.82–7.52 (m., 53H, pyridine, Bph4, PPh3), 7.95 (d, 1H, JH2,1
=
8 Hz, H1), 8.35 (s, 1H, H5). Anal. Calcd. for C70H63BCuN3OP2
(%): C, 76.53; H, 5.78; N, 3.82. Found: C, 76.55; H, 5.77; N,
3.82.
RESULTS AND DISCUSSION
General Characterization
(d, 1H, JH3,4 = 9.2 Hz, H4), 7.31 (dd, 1H, JH3,4 = 9.2, JH3,2
=
The IR spectra of the free ligand exhibit ν(C N) at
1621 cm−1. In complexes, the ν(C N) appears at 1580–2 cm−1
and is red shifted by 40 cm−1. This has been attributed to the
presence of d(Cu)→ π∗(ligand) back-bonding.[29,30]
11.5 Hz, H3), 7.76 (t, 1H, JH2,1 = 12.7, JH2,3 = 11.5 Hz, H2),
8.10 (d, 1H, JH1,2 = 12.7 Hz, H1), 8.21 (s, 1H, H5). Anal. Calcd.
for C10H13N3O (%): C, 62.81; H, 6.85; N, 21.97. Found: C,
62.83; H, 6.87; N, 21.95.
The electronic spectra of the complexes were recorded in
chloroform solution in the range 700–200 nm. The visible
range of the spectrum is dominated by metal-to-ligand charge
transfer (MLCT) transition, which is a characteristic feature
of the copper(I) complexes when bonded with a conjugated
organic chromophore.[31,32] A similar situation is observed in
Cu(NN)+2 complexes.[33] This is likely for a tetrahedrally dis-
torted Cu(NN)+2 coordination sphere. A single crystal X-ray
structural study supports this behavior (vide infra). The ab-
sorption spectrum of [Cu(4-ampc)2]BPh4 1 in chloroform fea-
tures a band with a true maximum at 485 nm. The [Cu(4-
ampc)(PPh3)2]BPh4 2 shows a clear shoulder at 390 nm, which
is shifted considerably (ca. 95 nm) relative to complex 1. A sim-
ilar shift has been reported in going from [Cu(dmp)2]+ (λMLCT
= 454 nm) to [Cu(dmp)(PPh3)2]+ (λMLCT = 365 nm).[34] Addi-
tional absorption bands are also observed in the spectra of 1 and
2 in chloroform in the UV region. The intensity of these bands
is consistent with its being ligand-centered π → π∗ or/and
charge-transfer transitions.
Synthesis of bis((Morpholin-4-yl-Pyridin-2-Ylmethylene-
Amine)Copper(I) Tetraphenylborate,
[Cu(4-ampc)2]BPh4, 1
To
a
stirring solution of morpholin-4-yl-pyridin-2-
ylmethylene-amine (19.1 mg, 0.1 mmol) in 5 mL acetonitrile
was added [Cu(CH3CN)4]BPh4 (27.4 mg, 0.05 mmol) in 5 mL
acetonitrile and stirred for 10 min. The solution turned orange
rapidly. The volume of the solvent was reduced under vacuum
to about 4 mL. The diffusion of diethyl ether vapor into the con-
centrated solution gave orange crystals. The resulting crystals
were filtered off and washed with a mixture of diethylether-
acetonitrile (9:1 v/v) and dried under vacuum. Yield: 92%. IR
1
data (KBr pellets, cm−1): 1582 (C N). H NMR (CDCl3; δ):
δ = 3.15–3.30 (m, 8H, CH2 N CH2 ), 3.68–3.71 (m, 8H,
CH2 O CH2 ), 6.86 (t. 8H, para H of BPh4), 7.03 (m, 8H,
meta H of BPh4), 7.20 (d, 2H, JH3,4 = 9.5 Hz, H4), 7.35 (dd,
2H, JH3,4 = 9.5, JH3,2 = 11.5 Hz, H3), 7.53 (b. 8H, meta H

600
DEHGHANPOUR AND ROMINGER
TABLE 1
Crystal data and structure refinement for 1
Empirical formula
C44H46BCuN6O2
Formula weight
Temperature
Wavelength
Crystal system
Space group
Z
765.22
200(2) K
0.71073 A
monoclinic
P21/c
˚
4
α = 90◦
˚
˚
a = 11.8431(6) A
b = 17.6213(9) A
β = 106.120(1)◦
γ = 90◦
˚
c = 18.9454(10) A
3
˚
Volume
3798.3(3) A
Density (calculated)
Absorption coefficient
Crystal shape
Crystal size
Crystal colour
1.34 g/cm3
0.62 mm−1
polyhedron
0.25 × 0.11 × 0.07 mm3
Orange
Theta range for data collection
Index ranges
1.8 to 28.4◦
15 ≤ h ≤ 15, 23 ≤ k ≤ 23, 25 ≤ l ≤ 25
Reflections collected
Independent reflections
Observed reflections
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices (I > 2σ(I))
Largest diff. peak and hole
39,850
9485 (R(int) = 0.0548)
7211 (I > 2σ(I))
Semiempirical from equivalents
0.96 and 0.86
Full matrix least squares on F2
9485/99/482
1.09
R1 = 0.066, wR2 = 0.137
−3
˚
1.27 and −0.51 eA
The 1H NMR spectra and peak assignments are presented in
the experimental section. These peaks are assigned based on the
splitting of the resonance signals, spin-coupling constants, and
the literature and are clearly in accordance with the molecular
structure determined by X-ray crystal structure analysis. The
spectra of the ligand are clearly divided into two portions; the
downfield part is due to pyridine and imine protons (1–5-H)
and the upfield signals refer to alkyl protons. Aside from the
aromatic H-atoms, which appear at 7.18–8.20 ppm in the ligand,
the imine proton appears as a singlet at 8.21 ppm in the ligand.
The multiplet peak at about 3.65 ppm in the ligand is assigned
to the proton in vicinity of oxygen atom of morpholine ring.
The other alkyl protons appear in 3.15 ppm as multiplet. The 1H
resonances of the coordinated ligand are commonly observed
in complexes 1 and 2. In complex 2, however, the aromatic H
atoms of the coordinated Ph3P ligands and BPh4 anion overlap
to some extent with those of the phenyl H atoms of the ligand.
The downfield shift of the iminic protons relative to the free
ligands can be attributed to the deshielding effect resulting from
the coordination of the ligands.[30]
TABLE 2
◦
˚
Selected bond length (A) and bond angle ( ) of 1
Cu1-N2
Cu1-N1
Cu1-N8
N21-Cu1-N1
2.011(2)
2.018(2)
2.069(2)
132.20(9)
Cu1-N28
N8-N11
C7-N8
C6-N1-C2
C6-N1-Cu1
C2-N1-Cu1
C7-N8-N11
C7-N8-Cu1
2.068(2)
1.374(3)
1.281(3)
117.5(2)
130.3(2)
112.19(18)
120.9(2)
111.91(19)
N21-Cu1-N28 81.68(9)
N1-Cu1-N28
N21-Cu1-N8
N1-Cu1-N8
N28-Cu1-N8
N8-N11-C1
N8-N11-C16
119.14(9)
126.90(9)
81.10(9)
Crystal Structure of [Cu(4-ampc)2]BPh4, 1
121.24(9) N11-N8-Cu1 126.90(16)
118.2(2) C12-N11-C16
112.0(2) C13-O14-C15
The crystallographic data are summarized in Table 1 and
selected bond distances and angles are given in Table 2. No
classical H-bonding occurs in this crystal structure. A view of
114.0(2)
108.1(2)

SPECTRAL CHARACTERIZATION
601
and comparison of the dihedral angles between the chelate rings
and pyridine groups indicates the coplanarity of these moieties,
˚
resulting in a bite size of 2.66 A of d(N–N) for the chelating lig-
and. The environment of the imine and pyridine nitrogen atoms
is planar. The planarity is measured by three N atom bond angles
(ꢀN). For 1, the average sum of these angles is 360◦ for N atoms.
Despite the fact that the nitrogen atoms in 1 are sp2 hybridized,
some strain in the chelate ring is suggested by the deviation from
the 120◦ angle about the nitrogen, Cu1–N1–C2 (112.19(18)◦),
C6–N1–Cu1 (130.3(2)◦), N11–N8–Cu1 (126.90(16)◦), C7–N8–
Cu1 (111.91(19)◦), C26–N21–Cu1 (130.6(2)◦), C22–N21–Cu1
(111.72(18)◦), C27–N28–N31 (121.4(3)◦), and C27–N28–Cu1
(111.97(19)◦). The morpholine rings in 1 adopt a chair confor-
mation but one of the two morpholine rings is disordered over
two positions, with the occupancy factors refined to 67:33.
Electrochemistry
The electrochemical behavior of the complexes was exam-
ined using cyclic voltammetry in CH2Cl2. The ligand 4-ampc is
electroinactive in the working potential region. Complex 1 show
a quasireversible CuII/I couple with an Ecp of 0.47 V (Figure 3).
The ratio of the anodic and cathodic peak currents, (ipa/ipc),
approaches one as the scan rate increases and the peak-to-peak
separation varies from 200 to 255 mV, as the scan rate is changed
from 50 to 500 mV/s.[35] The cyclic voltammogram of complex
2 in CH2Cl2 displays only one anodic peak (Ecp = 0.85 V). The
corresponding cathodic peak was not observed even under fast
scan-rate conditions. This is probably due to an irreversible
chemical reaction following the electron-transfer process.
The CuII/I potential in a CuIN4 chromophore is believed to
increase with increasing the π-acidity of the ligands and the re-
sistance to tetrahedral distortion occurring in the corresponding
CuIIN4 chromophore.[36−38] Although a higher degree of conju-
gation exists in 1 relative to 2, the existence of bulkier ligands
in 2 that prevent the inner-sphere reorganization to a flattened
tetrahedral, more appropriate to CuII oxidation state, plays a
key role in shifting the oxidation potential to higher values for
complex 2 relative to 1.
FIG. 2. ORTEPviewof thecrystalstructureof [Cu(4-ampc)2]BPh4 1 showing
the atom-labeling scheme. The thermal ellipsoids enclose 50% of the electronic
density. Hydrogen atoms are omitted for clarity. The major component of the
disordered cation (66%) was shown.
the cation of complex 1, including the atom numbering scheme,
is illustrated in Figure 2. While a tetrahedral geometry might
be expected for a four-coordinated copper(I) center, the coordi-
nation sphere around the metal ion in this complex is distorted
by the restricting bite angles of the chelating ligand. The in-
traligand N1–Cu–N8 and N1–Cu–N8 angles are much less than
109.5◦, being only 81.10(9)◦ and 81.68(9)◦, respectively. On the
contrary, the N21-Cu1-N1 and N21-Cu1-N8 angles (132.20(9)◦,
126.90(9)◦) are much larger than those of a tetrahedral complex
˚
(vide supra). The average Cu N bond distance (2.042 A) is sim-
˚
ilar to that found in the [Cu(dpdmp)2]+ cation (2.047 A) at room
temperature[32] and other Cu(I) pseudotetrahedral complexes
[30]
˚
(typical Cu–Nav = 2.055 A).
The average value for the di-
hedral angles of N1–C2–C7–N8 and N21–C22–C27–N28 is 2◦,
FIG. 3. Cyclic voltammograms of [Cu(4-ampc)2]BPh4 1 and [Cu(4-ampc)(PPh3)2]BPh4, 2 in CH2Cl2 at 293 K. Scan rate: 50 mVs−1. (1) c = 2 × 10−3
,
(2) c = 2.5 × 10−3
.

602
DEHGHANPOUR AND ROMINGER
CONCLUSION
17. Everly, R.M., and McMillin, D.R. Reinvestigation of the absorbing and
emitting charge-transfer excited-states of [Cu(NN)2]+ systems. J. Phys.
Chem., 1991, 95, 9071–9075.
The CuI complexes show pseudotetrahedral symmetry, and
1H-NMR data support the existence of CuI in 1 and 2. The po-
sition of the MLCT changes considerably and is blue-shifted by
95 nm, when one of the 4-ampc ligands is replaced by two Ph3P
molecules. Additional steric hindrance in complex 2 relative to
1 results in a more positive CuII/I redox potential.
18. Miller, M.T., Gantzel, P.K., and Karpishin, T.B. Effects of sterics and elec-
tronic delocalization on the photophysical, structural, and electrochemical
properties of 2,9-disubstituted 1,10-phenanthroline copper(I) complexes.
Inorg. Chem., 1999, 38, 3414–3422.
19. Desvergnes-Breuil, V., Hebbe, V., Dietrich-Buchecker, C., Sauvage, J.P.,
and Lacour, J. NMR evaluation of the configurational stability of Cu(I)
complexes. Inorg. Chem., 2003, 42, 255–257.
20. Amirnasr, M., Kickelbick, G., and Dehghanpour, S. Synthe-
sis, characterization, and X-ray crystal structures of Bis[N-(3,3-
diphenylallylidene)quinolin-8-amine-κN,κN8]copper(1+) Tetraphenyl-
borate(1−) ([Cu(dpa-qa)2]BPh4) and Bis[N,Nꢀ-bis(3,3-diphenyl-
allylidene)-[1,1ꢀ-biphenyl]-2,2ꢀ-diamine-κN, κNꢀ]copper(1+)perchlorate
([Cu(bdpa-bda)2]ClO4·3 H2O). Helv. Chim. Acta., 2006, 89, 274–284.
21. Miller, M.T., Gantzel, P.K., and Karpishin, T.B. Untersuchung eines photo-
lumineszierenden Kupfer(I)-Komplexkations mit außergewo¨hnlich hohem
CuII/CuI-Redoxpotential: [Cu(bfp)2]+ (bfp=2,9-Bis(trifluormethyl)-1,10-
phenanthrolin). Angew. Chem., 1998, 110, 1659–1661.
22. Meghdadi, S., Amirnasr, M., Schenk, K.J. and Dehghanpour, S. Syn-
thesis, characterization, and crystal structures of [Cu(ca2en)2]ClO4, and
[Cu(ca2en)(PPh3)2]ClO4. complexes. Helv. Chim. Acta., 2002, 85, 2807–
2816.
23. Hadjikhani, R., Dehghanpour, S., Mahmoudi, A. and Mojahed, F.
Bis[N,Nꢀ-bis(2-nitrocinnamaldehyde)phenylenediimine]copper(I) perchlo-
rate. Z. Anorg. Allg. Chem., 2006, 632, 723–725.
REFERENCES
1. Cunningham, C.T., Cunningham, K.L.H., Michalec, J.F., and McMillin,
D.R. Cooperative substituent effects on the excited states of copper phenan-
throlines. Inorg. Chem., 1999, 38, 4388–4392.
2. McMillan, D.R., Kirchhoff, J.R., and Goodwin, K.V. Exciplex quenching
of photo-excited copper complexes. Coord. Chem. Rev., 1985, 64, 83–92.
3. Malmstrom, B.G., Williams, R.J.P., De Silva, J.R.R.F. New Trends in
Bioinorganic Chemistry; Academic Press: New York, 1978.
4. Armaroli, N., Photoactive mono- and polynuclear Cu(I)-phenanthrolines.
A viable alternative to Ru(II)-polypyridines. Chem. Soc. Rev., 2001, 30,
113–124.
5. Hogan, G.A., Gallo, A.A., Nicholas, K.M., and Srivastava, R.S. Cu(I)-
catalyzed allylic amination of olefins. Tetrahedron Lett., 2002, 43, 9505–
9508.
6. Mahadevan, S., and Palaniandavar, M. Spectroscopic and voltammetric
studies on copper complexes of 2,9-dimethyl-1,10-phenanthrolines bound
to calf thymus DNA. Inorg. Chem., 1998, 37, 693–700.
24. Perrin, D.D., Armarego, W.L., and Perrin, D.R. Purification of Laboratory
Chemicals, 2nd Ed,.; Pergamon: New York, 1990.
7. Liu, F., Meadows, K.A., and McMillin, D.R. Binding studies of Cu(BCP)2+
and Cu(DMP)+2 —DNA elongation without interaction of Cu(BCP)+2 . J.
Am. Chem. Soc., 1993, 115, 6699–6704.
25. Hemmerich, P., and Sigwart, C. Cu(CH3CN)þ+2 , ein Mittel zum Studium
homogener Reaktionen des einwertigen Kupfers in wassriger Losung. Ex-
perientia, 1963, 15(9), 488–489.
8. Ruthkosky, M., Kelly, C.A., Castellano, F.N., and Meyer, G.J., Electron
energy transfer from CuI MLCT excited states. Coord. Chem. Rev., 1998, 26. Sheldrick, G.M. Program SADABS 2006/1 for Absorption Correction;
171, 309–322.
Bruker Analytical X-ray-Division: Madison, WI, 2006.
27. Sheldrick, G.M. Software Package SHELXTL V6.10 for Structure Solu-
tion and Refinement; Bruker Analytical X-ray Division: Madison, WI,
2001.
28. Wiley, R.H., White, H.K., and Irick, G. Alkylidene- and arylide-
neaminomorpholines. J. Org. Chem., 1959, 24, 1784–1786.
29. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination
Complexes, 4th Edn.; Wiley: New York, 1992.
30. Dehghanpour, S., Kempe, R., Balireddi, S., Fotouhia, L., Tabasia, F., Moja-
hed, F., and Salek, S. Synthesis, characterization and X-ray crystal structures
of [Cu(ncaen)2]ClO4 and [Cu(nca2en)(PPh3)2]BPh4 complexes. Z. Anorg.
Allg. Chem., 2006, 632, 2321–2325.
31. Del Paggio, A.A., and McMillin, D.R. Substituent effects and the photo-
luminescence of Cu(PPh3)2(NN)+ systems. Inorg. Chem., 1983, 22, 691–
692.
9. Sakaki, S., Kuroki, T., and Hamada, T. Synthesis of a new copper(I) com-
plex, [Cu(tmdcbpy)2]+ (tmdcbpy=4,4ꢀ,6,6ꢀ-tetramethyl-2,2ꢀ-bipyridine-
5,5ꢀ-dicarboxylic acid), and its application to solar cells. J. Chem Soc.,
Dalton Trans., 2002, 6, 840–842.
10. Gushurst, A.K.I., McMillin, D.R., Dietrich-Buchecker, C.O., and Sauvage,
J.P. Comparative studies of the photophysical properties of copper phenan-
throlines: From Cu(dmp)+2 to the copper(I) catenates. Inorg. Chem., 1989,
28, 4070–4072.
11. Ichinaga, A.K., Kirchhof, J.R., McMillin, D.R., Dietrich-Buchecker, C.O.,
Marnot, P.A., and Sauvage, J.P. Charge-transfer absorption and emission of
Cu(NN)2+ systems. Inorg. Chem., 1987, 26, 4290–4292.
12. Ruthkosky, M., Kelly, C.A., Zaros, M.C., and Meyer, G.J. Long-lived
charge-separated states following excitation of Cu(I) donor-acceptor com-
pounds. J. Am. Chem. Soc., 1997, 119, 12004–12005.
13. Dehghanpour, S., Bouslimani, N., Welter, R., and Mojahed, F. Synthesis,
spectral characterization, properties and structures of copper(I) complexes
containing novel bidentate iminopyridine ligands. Polyhedron, 2007, 26,
154–162.
14. Goswami, S., Kharmawphlang, W., Deb, A.K., and Peng, S.M. Monovalent
copper complexes of N-aryl-pyridine-2-aldimine. Synthesis, characteriza-
tion and structure. Polyhedron, 1996, 20, 3635–3641.
15. Dominey, R.N., Hauser, B., Hubbard, J., and Dunham, J. Structural, spec-
tral and charge-transfer properties of ClRe(CO)3(2-PP) [2-PP = N-(2-
pyridinylmethylene)phenylamine] and ClRe(CO)3(2-PC) [2-PC = N-(2-
pyridinylene)cyclohexylamine]. Inorg. Chem., 1991, 30, 4754–4758.
16. Dose, E.V., and Wilson, L.J. Synthesis and electrochemical and pho-
toemission properties of mononuclear and binuclear ruthenium(II) com-
plexes containing 2,2ꢀ-bipyridine, 2,9-dimethyl-1,10-phenanthroline, 2,2ꢀ-
32. Miller, M.T., Gantzel, P.K., and Karpishin, T.B. Structures of the copper(I)
and copper(II) complexes of 2,9-diphenyl-1,10-phenanthroline: Implica-
tions for excited-state. Inorg. Chem., 1998, 37, 2285–2290.
33. Bradwell, D.A., Jeffery, J.C., Otter, C.A., and Ward, M.D. The crystal
structure of [Cu(Ph2bipy)2][BF4].CH2Cl2 (Ph2bipy=6,6ꢀ-diphenyl-2,2ꢀ-
bipyridine). Polyhedron, 1996, 15, 191–194.
34. Rader, R.A., McMillin, D.R., Buckner, M.T., Matthews, T.G., Casadonte,
D.J., Lengel, R.K., Whittaker, S.B., Darmon, L.M., and Lytle, F.E.
Photostudies of 2,2ꢀ-bipyridine bis(triphenylphosphine)copper1+, 1,10-
phenanthroline bis(triphenylphosphine)copper1+, and 2,9-dimethyl-1,10-
phenanthroline bis(triphenylphosphine)copper1+ in solution and in rigid,
low-temperature glasses. Simultaneous multiple emissions from intrali-
gand and charge-transfer states. J. Am. Chem. Soc., 1981, 103, 5906–
5912.
bipyrimidine, 2,2ꢀ-biimidazole, and 2-pyridinecarboxaldimine ligands. In- 35. Bard, A.J., and Faulkner, L.R. Electrochemical Methods, Fundamentals
org. Chem., 1978, 9, 2660–2666.
and Applications; Wiley: New York, 1980.

SPECTRAL CHARACTERIZATION
603
36. Santra, P.K., Das, D., Misra, T.K., Roy, R., Sinha, C., and
Peng, S.-M. Chemistry of azopyrimidines—Synthesis. spectral char-
acterization, electrochemistry and X-ray crystal structure of bis[2-
systems in fluid solution. Crystal and molecular structures of [Cu(dmp)
(PPh3)2]NO3 and [Cu(phen)(PPh3)2]NO3.1.5EtOH. Inorg. Chem., 1985,
24, 3928–3933.
(arylazo)pyrimidine] complexes of copper(I). Polyhedron, 1999, 18, 1909– 38. Miller, M.T., Gantzel, P.K., and Karpishin, T.B. A photoluminescent
1915.
copper(I) complex with an exceptionally high CuII/CuI redox potential:
[Cu(bfp)2)]+ (bfp = 2,9-bis(trifluoromethyl)-1,10-phenanthroline). Angew.
Chem. Int. Ed., 1998, 37, 1556–1558.
37. Kirchho, J.R., McMillin, D.R., Robinson, W.R., Powell, D.R., T. McKen-
zie, A., and Chen, S. Steric effects and the behavior of Cu(NN)(PPh3)2+