Heteroligand copper(I) complexes of N-thiophosphorylated thioureas and phosphanes: Versatile structures and luminescence

Article abstract of DOI:10.1016/j.ica.2011.01.035

Reaction of the potassium salts of (EtO)₂P(O)CH ₂C₆H₄-4-(NHC(S)NHP(S)(OiPr)₂) (HL^I), (CH₂NHC(S)NHP(S)(OiPr)₂)₂ (H₂L^II) or cyclam(C(S)N

Full text of DOI:10.1016/j.ica.2011.01.035

Inorganica Chimica Acta 370 (2011) 59–64
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Inorganica Chimica Acta
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Heteroligand copper(I) complexes of N-thiophosphorylated thioureas and
phosphanes: Versatile structures and luminescence
b
a
Damir A. Safin a, Maria G. Babashkina a, , Michael Bolte , Martin Köckerling
⇑
a Institut für Chemie, Anorganische Festkörperchemie, Albert-Einstein-Str. 3a, D-18059 Rostock, Germany
b Institut für Anorganische Chemie, J.-W.-Goethe-Universität, Frankfurt/Main, Germany
a r t i c l e i n f o
a b s t r a c t
Reaction of the potassium salts of (EtO)2P(O)CH2C6H4-4-(NHC(S)NHP(S)(OiPr)2) (HLI), (CH2NHC(S)NHP(S)
(OiPr)2)2 (H2LII) or cyclam(C(S)NHP(S)(OiPr)2)4 (H4LIII) with [Cu(PPh3)3I] or a mixture of CuI and
Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 leads to [Cu(PPh3)LI] (1),
[Cu2(Ph2PCH2PPh2)2LII] (2), [Cu{Ph2P(CH2)2PPh2}LI] (3), [Cu{Ph2P(CH2)3PPh2}LI] (4), [Cu{Ph2P(C5H4-
FeC5H4)PPh2}LI] (5), [Cu2(PPh3)2LII] (6), [Cu2(Ph2PCH2PPh2)LII] (7), [Cu2{Ph2P(CH2)2PPh2}2LII] (8),
[Cu2{Ph2P(CH2)3PPh2}2LII] (9), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (10), [Cu8(Ph2PCH2PPh2)8LIIII4] (11),
[Cu4{Ph2P(CH2)2PPh2}4LIII] (12), [Cu4{Ph2P(CH2)3PPh2}4LIII] (13) or [Cu4{Ph2P(C5H4FeC5H4)PPh2}4LIII] (14)
complexes. The structures of these compounds were investigated by IR, 1H, 31P{1H} NMR spectroscopy;
their compositions were examined by microanalysis. The luminescent properties of the complexes 1–14
in the solid state are reported.
Article history:
Received 27 September 2010
Received in revised form 21 December 2010
Accepted 11 January 2011
Available online 1 February 2011
Keywords:
Coordination chemistry
Copper
N-Thiophosphoryl thiourea
Phosphane
Ó 2011 Elsevier B.V. All rights reserved.
Luminescence
1. Introduction
Ph2P(CH2)1–3PPh2 and Ph2P(C5H4FeC5H4)PPh2 phosphanes. The
reaction of alkaline salts of the tetrakis-thiourea, containing a cy-
Mono-, oligo- and polynuclear Cu(I) complexes [Cux(phos-
phane)yLigx] with neutral monodentate tertiary phosphanes PR3
or bidentate bis-phosphanes R2P–Z–PR2 (Z = (CH2)n, C5H4FeC5H4,
arylene, etc.) have been extensively investigated [1]. This type of
Cu(I) complexes shows an interesting structural variety and pos-
sess a number of various aggregates and associates both in solution
and the solid state, and hence a number of properties (e.g. lumines-
cent properties). The structure and electronic properties of the
ligand Lig is also very important due to the fine-tuning of the struc-
ture and properties of a complex. In this connection the chalcogen-
containing ligands are attractive since these donor atoms are
known to adopt different coordination modes. The sulfur-contain-
ing ligands are the most widely used among them [1a,2]. This is,
probably, due to the easy ways to synthesis such type of
compounds compared to other chalcogen-containing ligands. A
number of mixed-ligand Cu(I) complexes, containing both aryl-
substituted pnictines and cyclic thioureas or pyridine thiolates,
are also described [1a,2a]. Combination of these two types of
ligands might lead to interesting and unusual photophysical and
electrochemical properties [3].
clam fragment cyclam(C(S)NHP(S)(OiPr)2)4, with [Cu(PPh3)3I] leads
to the tetranuclear Cu(I) complex [{Cu(PPh3)2}4Lig] (Chart 1) [5].
Furthermore, urea derivatives of cyclen and cyclam have, to the
best of our knowledge, been reported so far in the literature by
only two examples [5,6].
In this contribution we describe mixed-ligand Cu(I) complexes of
(EtO)2P(O)CH2C6H4-4-(NHC(S)NHP(S)(OiPr)2) (HLI), (CH2NHC(S)-
NHP(S)(OiPr)2)2 (H2LII) or cyclam(C(S)NHP(S)(OiPr)2)4 (H4LIII) and
phosphanes (PPh3, Ph2P(CH2)1–3PPh2, Ph2P(C5H4FeC5H4)PPh2).
2. Results and discussion
N-Thiophosphorylated thioureas HLI, H2LII and H4LIII were pre-
pared as described previously [5,4d,7]. Reaction of the potassium
salts of HLI, H2LI or H4LII with [Cu(PPh3)3I] or a mixture of CuI
and Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/
CH2Cl2 leads to [Cu(PPh3)LI] (1), [Cu2(Ph2PCH2PPh2)2LII] (2),
[Cu{Ph2P(CH2)2PPh2}LI] (3), [Cu{Ph2P(CH2)3PPh2}LI] (4), [Cu{Ph2P-
(C5H4FeC5H4)PPh2}LI] (5) (Scheme 1), [Cu2(PPh3)2LII] (6), [Cu2(Ph2
PCH2PPh2)LII] (7), [Cu2{Ph2P(CH2)2PPh2}2LII] (8), [Cu2{Ph2P(CH2)3
PPh2}2LII] (9), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (10) (Scheme 2),
[Cu8(Ph2PCH2PPh2)8LIIII4] (11), [Cu4{Ph2P(CH2)2PPh2}4LIII] (12), [Cu4
{Ph2P(CH2)3PPh2}4LIII] (13) or [Cu4{Ph2P(C5H4FeC5H4)PPh2}4LIII]
(14) (Scheme 3) complexes.
Recently, we have described mixed-ligand Cu(I) complexes
incorporating a number of N-thiophosphorylated thioureas or thi-
obenzamides, RC(S)NHP(S)(OiPr)2 [4], and triphenylphosphane or
⇑
The complexes obtained are colorless crystalline powders,
soluble in acetone, benzene, dichloromethane, DMSO, DMF and
Corresponding author.
E-mail address: maria.babashkina@ksu.ru (M.G. Babashkina).
0020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.01.035

60
D.A. Safin et al. / Inorganica Chimica Acta 370 (2011) 59–64
In our recent publications we have published the syntheses and
crystal structures of similar complexes [Cu2(Ph2PCH2PPh2){H2
NC(S)NP(S)(OiPr)2}2] (15), [Cu2(Ph2PCH2PPh2){o-C6H4(NHC(S)
NP(S)(OiPr)2)2}] [4i] (16) and [Cu2(Ph2PCH2PPh2)2{RNHC(S)NP
(S)(OiPr)2}I] (R = Me, 17; Ph, 18) [4j]. Unfortunately, after numer-
ous attempts we were not successful to get X-ray suitable crystals
of the complexes. However, according to the NMR and lumines-
cence data (see below), and elemental analyses the structure of
the chelate backbones of 2, 7 and 11 are similar to the previously
described complexes 15–18. The formation of 2, 7 and 11 can be
explained by the rather small bite angle expected for Ph2PCH2PPh2.
The IR spectrum of HLI contains a band at 649 cmÀ1 for the P@S
group. It is shifted to lower wavenumbers (597–623 cmÀ1) in the
spectra of 1–5 due to the coordination with the cation. The shift
is 42–52 cmÀ1 in 1 and 3–5, while the shift in the spectrum of 2
is 26 cmÀ1, which might be due to the coordination of two phos-
phanes. The IR bands of P@S in the spectra of 6, 8–10, and 12–14
are shifted by 23–30 and 33–38 cmÀ1 to lower wavenumbers rela-
tively to the parent ligands H2LII and H4LIII, respectively [5,7]. The
P@S band in the IR spectra of 7 and 11 is also shifted to lower
wavenumbers relatively to H2LII and H4LIII; however, the shift is
19 and 14 cmÀ1, respectively. The appearance of the new broad
and intense band at 1517–1572 cmÀ1, due to the conjugated SCN
group, also proves the formation of complexes. The presence of
the substituted POC groups in HLI and 1–14 can be established
from the IR spectra by their absorption bands at 998–1014 cmÀ1
[8]. Two bands for the arylNH and P(S)NH groups at 3144 and
O
N
O
N
O
Ph Ph
Ph Ph O
Ph
P
S
P
S
P
Ph
P
Cu
Cu
Ph
P
S
S
P
Ph
N
N
Ph Ph
Ph Ph
Ph Ph
Ph Ph
N
N
Ph
Ph
P
S
S
S
P
Ph
Cu
N
N
Cu
P
P
P
S
P
Ph
Ph Ph O
O
O
O
Ph Ph
Chart 1.
insoluble in n-hexane and water. 1H, 31P{1H} NMR data indicate
that the deprotonated thioureas LI–III are coordinated through the
sulfur atoms of the thiocarbonyl and thiophosphoryl groups in all
the present cases studied.
It is noteworthy that the reaction of the potassium salts KLI,
K2LII and K4LIII with a mixture of CuI and Ph2PCH2PPh2 leads to
the formation of the binuclear (2, 7) or octanuclear (11) complexes.
H
N
O
O
1
(EtO)2P CH2
O
N
P
S
S
Cu
PPh3
H
N
Ph2PCH2PPh2
N
P
O
O
2
(EtO)2P CH2
O
I
S
S
Cu
Cu
Ph2P
PPh2
Ph2P
PPh2
1) KOH
2) [Cu(PPh3)3I]
or CuI + phosphine Ph2P(CH2)2PPh2
H
H
H
N
N
P
O
O
N
O
O
3
4
5
(EtO)2P CH2
O
N
(EtO)2P CH2
O
P
S
S
S
S
Cu
Ph2P
PPh2
HLI
H
Ph2P(CH2)3PPh2
N
P
O
O
(EtO)2P CH2
O
N
S
S
Cu
Ph2P
PPh2
H
Ph2P(C5H4FeC5H4)PPh2
N
O
(EtO)2P CH2
O
N
P
O
S
S
Cu
Ph2P
PPh2
Fe
Scheme 1.

D.A. Safin et al. / Inorganica Chimica Acta 370 (2011) 59–64
61
O
N
N
O
O
6
P
S
N
N
P
S
O
H
H
S
S
Cu
Cu
Ph3P
PPh3
Ph3P
PPh3
O
P
N
N
O
P
Ph2PCH2PPh2
7
N
N
O
S
O
H
H
Cu
PPh2
S
S
S
Cu
Ph2P
1) KOH
2) [Cu(PPh3)3I]
or CuI + phosphine Ph2P(CH2)2PPh2
H
N
H
N
O
P
N
N
O
O
O
O
O
8
N
N
P
O
S
P
S
N
N
P
S
O
S
H
H
H
H
S
S
S
S
Cu
Cu
H2LII
Ph2P
PPh2
Ph2P
PPh2
O
P
N
N
O
Ph2P(CH2)3PPh2
9
N
N
P
O
S
O
S
H
H
S
S
Cu
Cu
Ph2P
PPh2
Ph2P
PPh2
O
P
N
N
O
P
10
N
N
O
S
O
Ph2P(C5H4FeC5H4)PPh2
H
H
S
S
S
Cu
Cu
Ph2P
PPh2
Ph2P
PPh2
Fe
Fe
Scheme 2.
3281 cmÀ1 are observed in the IR spectrum of HLI, whereas a
unique band at 3208–3276 cmÀ1 corresponding to the arylNH
group was found in the spectra of 1–5. It should be noted that
the band of the arylNH group in the IR spectra of 1 and 2 is ob-
served at 3208 and 3214 cmÀ1, respectively, and in the character-
istic region of amide protons participating in hydrogen bonding.
The IR bands of the NH group in the spectra of 6 and 8–10 were
observed at 3371–3397 cmÀ1, shifted by 43–69 cmÀ1 to lower
wavenumbers relatively to H2LII (3440 cmÀ1) [5], while the same
band in the spectrum of 7 appears at 3204 cmÀ1. The signal for
the NH group is absent in the IR spectra of the complexes 11–14.
It should be noted that in the IR spectra of 2–5 the band
corresponding to the P@O fragment of the P(O)CH2 group occurs
between 1198 and 1208 cmÀ1, that is in the same region as in
the free ligand (1211 cmÀ1). This confirms the absence of coordina-
tion of the P@O group in the P(O)CH2 fragment of the complexes
2–5. In the IR spectrum of 1 the absorption band of the P@O group
is observed at 1158 cmÀ1, and considerably shifted to higher
frequencies compared to the spectrum of the parent ligand. This
might be due to the formation of hydrogen bonds.
6–14, the resonances in the range 50.7–57.2 ppm correspond to
the phosphorus atom of the thiophosphoryl groups [9]. The signal
of the phosphorus atom of PPh3 in the spectrum of the complex 6
was found at À1.9 ppm, while the signals for the phosphane phos-
phorus atoms in the 31P{1H} NMR spectra of the complexes 2–5
and 7–14 exhibit chemical shifts from À26.6 to À9.8 ppm.
Fast exchange between free and bound phosphane in solutions
of studied complexes results in phosphane signal broadening in the
31P{1H} NMR spectra, as was observed for the Cu(I) complexes with
N-(thio)phosphorylated thioamides and thioureas [4,5].
The 1H NMR spectra of 2–14 contain a set of signals, corre-
sponding to the resulting product. The spectra contain signals for
the CH3 protons at 0.81–1.76 ppm and signals for the OCH, OCH2
and CH2N protons at 3.19–5.33 ppm. The signals for the C6H4 and
C6H5 protons in the spectra are shown as multiplets at
6.74–8.11 ppm. The P(O)CH2 protons doublet signal in the spectra
of 1–5 is at 3.08–3.15 ppm. The 1H NMR spectra of 2–4, 7–9 and
11–13 contain the signals for the CH2 protons of the correspond-
ing phosphane Ph2P(CH2)1–3PPh2 and cyclam (11–13) at
1.46–4.30 ppm, while the signals for the C5H4 protons in the
spectrum of 5, 10 and 14 are observed at 4.20–4.30 ppm. There is
a singlet for the arylNH proton at 6.61–6.89 ppm in the spectra
of the complexes 3–5. The same signal in the spectrum of 2 was
found at 9.85 ppm. This testifies about the hydrogen bonding in
the structure of 2. In the spectra of 6–11 the signals of the alkylNH
protons were observed at 6.16–7.99 ppm and overlapped with the
In the 31P{1H} NMR spectra of 1–5 the resonance for the phos-
phoryl and thiophosphoryl groups are shown at 27.2–27.8 and
55.0–56.2 ppm, respectively [9]. The signal corresponding to the
P@S group is low-field shifted, whereas the singlet for the P@O
group is practically at the same region relative to those in the par-
ent ligand HLI [4d]. In the 31P{1H} NMR spectra of the complexes

62
D.A. Safin et al. / Inorganica Chimica Acta 370 (2011) 59–64
Ph
Ph
Ph
O
O
N
O
N
O
Ph
P
P
S
S
P
P
Ph
P
Ph
Cu
Cu
Ph
P
Ph
P
P
Ph Ph
Ph Ph
O
O
N
O
N
O
S
S
Ph
Ph
Ph
Ph
P
S
P
P
P
P
S P
P
Cu
Cu
Ph
Cu
Cu
I
I
P
P
Ph
N
N
P
S
S P
Ph
Ph
Ph
Ph
Ph
Ph
Ph
N
N
Ph Ph
Ph Ph
N
N
P
P
P
Ph
I
I
Ph
Ph Ph
Ph Ph
Cu
Cu
N
N
P
Ph
P
Ph
S
S
P
S
S P
P
Ph
N
N
Cu
Cu
N
N
Cu
Cu
Ph
Ph
O
O
O
O
P
P
S
P
S
P
S
S P
P
P
P
P
S
S
Ph
Ph
O
O
O
O
O
Ph Ph O
O
O
O
O
Ph Ph
NH
NN
HN
Ph
Ph
S
S
1. KOH
2. CuI + phosphine
1. KOH
2. CuI + phosphine
11
13
N
N
S
S
Ph Ph
Ph Ph O
O
N
O
N
Ph Ph
Ph Ph O
O
N
O
N
NH
HN
S
S
P
P
P
S
S
P
P
S
P
S
P
P
P
O
O
Cu
Cu
O
O
Cu
Cu
Fe
Fe
Fe
Fe
P
S
S
P
P
S
S
P
N
N
N
N
Ph Ph
Ph Ph
Ph Ph
Ph Ph
III
L
H4
Ph Ph
Ph Ph
Ph Ph
Ph Ph
N
N
N
N
P
S
S
P
P
S
S P
Cu
N
N
Cu
Cu
N
N
Cu
P
S
P
S
P
P
S
S
P
P
P
Ph Ph O
O
O
O
Ph Ph
O
O
O
O
Ph Ph
Ph Ph
12
14
Scheme 3.
signals for the Ph protons. The signal for the NHP group proton is
absent in the 1H NMR spectra of 1–14. This confirms the presence
of the ligand in the anionic form in the structure of complexes.
The luminescent properties of 1–14 were investigated in the so-
lid state at room temperature. The data are listed in Table 1. From
the emission behavior we can define four different groups of com-
plexes. First, the two complexes 1 and 6, which show no emission
in the solid state. Second, the complexes 3–5, 8–10 and 12–14.
Their emission maxima vary only slightly between 466 and
487 nm. The complex 7, which contains Ph2PCH2PPh2 as a chelate
phosphane ligand, forms the third group and shows emission at
519 nm. The last group is formed by the two complexes 2 and
11, which also contain Ph2PCH2PPh2 as a chelate phosphane ligand,
and the iodine ligand, which is bound to one of the copper atoms
(Schemes 1 and 3). It is noteworthy that neither the parent ligands
HLI, H2LII and H4LIII, nor their corresponding potassium salts show
emission in the solid state at the same experimental conditions.
Emissions around 450–510 nm are typical of Cu–phosphane
containing chromophores with either ILCT (r–a ) or MLCT (d–
p
r⁄) excited states [10]. Therefore, we can assign the emission
(3ILCT or 3MLCT) from the observed energies and the marked
dependence on the type of the phosphane ligand (see last three
groups), although a 3p p⁄ contribution of the thiourea ligand an-
–
ions (LI–III) cannot be ruled out completely. The differences in the
emission spectra probably arise from the fact that while PPh3 can
only provide one type of
r–a transition, the chelate phosphane li-
p
gands additionally contain bridging alkyl or ferrocenyl groups. The
propensity to emit (or not) very probably depend on the geometry
of the Cu–phosphane chromophore, which is largely depending on
the chelate bite angle of the ligand. One interesting point in this re-
spect is the unusual emission for the complex 7, which might be
due to contributions from cluster-centered charge transfer transi-
tion in this binuclear aggregate, probably containing rather short
Cu1ÁÁÁCu2 distances, similar to 15 and 16 [4i]. Furthermore, the
emission spectra of the complexes 2 and 11, besides the blue emis-
sion band, which is in the same area as in the spectra of the com-
plexes 3–5, 8–10 and 12–14, contain the low energy band (Table
1). On the basis of these experiments we can draw the conclusion
that the presence of the iodine ligands in 2 and 11 are connected to
the observation of the long-wavelength emissions around 615 nm.
Presumably they originate from ligand (IÀ) to metal (Cu(I)) charge
transfer transition, similar to 17 and 18 [4j].
Table 1
Photophysical data for 1–14.
Complex
Emission maximum (nm)
1
2
3
No emission
448, 618
466
4
470
5
487
6
7
No emission
519
8
478
9
469
10
11
12
13
14
482
452, 614
461
463
486
3. Experimental
All chemicals and reagents were purchased from commercial
sources and used as received. All syntheses were carried out under

D.A. Safin et al. / Inorganica Chimica Acta 370 (2011) 59–64
63
ambient conditions. N-Thiophosphorylthiourea HLI, H2LII and H4LIII
and the complex 1 were prepared as previously described [5,4d,7].
(0.062 g, 1.1 mmol). A solution of [Cu(PPh3)3I] (0.977 g, 1.0 mmol)
in CH2Cl2 (25 mL) was added dropwise under vigorous stirring to
the resulting potassium salt. The mixture was stirred for an hour
and the resulting precipitate of KI was filtered off. The filtrate
was concentrated until crystallization began. Isolated crystals were
precipitated from a dichloromethane/n-hexane mixture 1:5 (v/v).
HLI: IR
m
(cmÀ1): 649 (P@S), 1009 (POC), 1211 (P@O), 1569
(S@C–N), 3144, 3281 (NH).
1: mp 127–128 °C (127 °C [4d]). IR
m
(cmÀ1): 597 (P@S), 998
(POC), 1158 (P@O), 1544 (SCN), 3208 (NH).
6: Yield 0.702 g (82%), mp 109–110 °C. IR
1001 (POC), 1529 (SCN), 3371 (NH). 1H NMR (CDCl3) d (ppm):
m
(cmÀ1): 610 (P@S),
3.1. Synthesis of 2–5
3
3
1.27 (d, JH,H = 6.0 Hz, 12H, CH3, iPr), 1.30 (d, JH,H = 6.1 Hz, 12H,
A suspension of HLI (0.241 g, 0.5 mmol) in aqueous ethanol
(35 mL) was mixed with an ethanol solution of potassium hydrox-
ide (0.031 g, 0.55 mmol). A mixture of CuI (0.095 g, 0.5 mmol) and
Ph2P(CH2)nPPh2 (n = 1, 0.192 g; n = 2, 0.199 g; n = 3, 0.206 g;
0.5 mmol) or Ph2P(C5H4FeC5H4)PPh2 (0.277 g, 0.5 mmol) in CH2Cl2
(25 mL) was refluxed for 0.5 h and then added dropwise under vig-
orous stirring to the resulting potassium salt. The mixture was stir-
red for an hour and the precipitate was filtered off. The filtrate was
concentrated until crystallization began. Isolated crystals were ob-
tained from a CH2Cl2/n-hexane mixture 1:5 (v/v).
CH3, iPr), 3.48 (br. s, 4H, CH2N), 4.73 (d. sept, JH,H = 6.0 Hz,
3
3JP,H = 10.9 Hz, 4H, OCH), 6.16 (br. s, 2H, NH), 7.28–7.46 (m, 60H,
Ph); 31P{1H} NMR (CDCl3) d (ppm): À1.9 (s, 4P, PPh3), 54.6 (s, 2P,
NPS). Anal. Calc. for C88H94Cu2N4O4P6S4 (1712.91): C, 61.71; H,
5.53; N, 3.27. Found: C, 61.83; H, 5.46; N, 3.21%.
3.3. Synthesis of 7–10
A suspension of H2LII (0.269 g, 0.5 mmol) in 96 % aqueous eth-
anol (35 mL) was mixed with an 96% ethanol solution of potassium
hydroxide (0.062 g, 1.1 mmol). A mixture of CuI (0.19 g, 1.0 mmol)
and Ph2P(CH2)nPPh2 (n = 1, 0.384 g; n = 2, 0.398 g; n = 3, 0.412 g;
1.0 mmol) or Ph2P(C5H4FeC5H4)PPh2 (0.554 g, 1.0 mmol) in CH2Cl2
(25 mL) was refluxed for 0.5 h and then added dropwise under vig-
orous stirring to the resulting potassium salt. The mixture was stir-
red for an hour and the precipitate of KI was filtered off. The filtrate
was concentrated until crystallization began. Isolated solid materi-
als were obtained from a dichloromethane/n-hexane mixture 1:3
(v/v).
2: Yield 0.275 g (73%), mp 204–205 °C. IR m
(cmÀ1): 623 (P@S),
1014 (POC), 1207 (P@O), 1567 (SCN), 3214 (NH). 1H NMR
(DMSO-d6) d (ppm): 1.07–1.34 (m, 18H, CH3, EtO + iPrO), 2.48
2
(br. s, 4H, CH2), 3.12 (d, JP,H = 21.3 Hz, 2H, CH2, P(O)CH2), 3.88–
4.06 (m, 4H, OCH2, EtO), 4.62 (d. sept, 3JH,H = 6.1 Hz,
3JPOCH = 10.0 Hz, 2H, OCH, iPrO), 7.07–7.84 (m, overlapping with
the solvent signal, C6H4 + C6H5), 9.85 (s, 1H, NH); 31P{1H} NMR
(DMSO-d6) d (ppm): À24.6 to À13.8 (m, 4P, PPh2), 27.8 (s, 1P,
P@O), 56.2 (s, 1P, P@S). Anal. Calc. for
C68H75Cu2IN2O5P6S2
(1504.31): C, 54.29; H, 5.03; N, 1.86. Found: C, 54.13; H, 5.09; N,
1.82%.
7: Yield 0.388 g (74%), mp 58–59 °C. IR m
(cmÀ1): 621 (P@S),
1004 (POC), 1572 (SCN), 3204 (NH). 1H NMR (CDCl3) d (ppm):
1.04–1.76 (m, 24H, CH3, iPr), 2.91 (br. s, 2H, CH2), 4.30–5.33 (m,
8H, OCH + CH2N), 6.79–7.59 (m, overlapped with the solvent sig-
nal, NH + Ph); 31P{1H} NMR (CDCl3) d (ppm): À9.8 (s, 2P, PPh2),
57.2 (s, 2P, NPS). Anal. Calc. for C41H56Cu2N4O4P4S4 (1048.15): C,
46.98; H, 5.39; N, 5.35. Found: C, 47.13; H, 5.28; N, 5.41%.
3: Yield 0.382 g (81%), mp 83–84 °C. IR
m
(cmÀ1): 602 (P@S),
1001 (POC), 1203 (P@O), 1553 (SCN), 3274 (NH). 1H NMR (CDCl3)
d (ppm): 1.12–1.33 (m, 18H, CH3, EtO + iPrO), 2.30 (br. s, 4H,
2
CH2), 3.08 (d, JP,H = 20.8 Hz, 2H, CH2, P(O)CH2), 3.81–3.99 (m, 4H,
3
3
OCH2, EtO), 4.75 (d. sept, JH,H = 6.2 Hz, JPOCH = 9.7 Hz, 2H, OCH,
iPrO), 6.72 (s, 1H, NH), 7.16–7.96 (m, overlapping with the solvent
signal, C6H4 + C6H5); 31P{1H} NMR (CDCl3) d (ppm): À12.8 (br. s, 2P,
PPh2), 27.3 (s, 1P, P@O), 55.3 (1P, P = S). Anal. Calc. for C44H55Cu-
N2O5P4S2 (943.49): C, 56.01; H, 5.88; N, 2.97. Found: C, 56.15; H,
5.93; N, 2.90%.
8: Yield 0.635 g (87%), mp 83–84 °C. IR
m
(cmÀ1): 611 (P@S),
1014 (POC), 1522 (SCN), 3386 (NH). 1H NMR (CDCl3) d (ppm):
1.28 (br. s, 24H, CH3, iPr), 2.27 (br. s, 8H, CH2), 3.47 (br. s, 4H,
CH2N), 4.69 (br. s, 4H, OCH), 6.82–7.99 (m, overlapped with the sol-
vent signal, NH + Ph); 31P{1H} NMR (CDCl3) d (ppm): À12.5 (br. s,
4P, PPh2), 53.7 (s, 2P, NPS). Anal. Calc. for C68H82Cu2N4O4P6S4
(1460.60): C, 55.92; H, 5.66; N, 3.84. Found: C, 55.79; H, 5.73; N,
3.80%.
4: Yield 0.455 g (95%), mp 70–71 °C. IR
m
(cmÀ1): 599 (P@S),
1007 (POC), 1208 (P@O), 1548 (SCN), 3269 (NH). 1H NMR (CDCl3)
d (ppm): 1.03–1.27 (m, 18H, CH3, EtO + iPrO), 2.38 (br. s, 4H,
2
CH2), 2.85 (br. s, 2H, CH2), 3.13 (d, JP,H = 20.4 Hz, 2H, CH2,
9: Yield 0.588 g (79%), mp 67–68 °C. IR m
(cmÀ1): 617 (P@S),
P(O)CH2), 3.91–4.08 (m, 4H, OCH2, EtO), 4.54 (d. sept, 3JH,H = 6.0 Hz,
3JPOCH = 10.3 Hz, 2H, OCH, iPrO), 6.61 (s, 1H, NH), 7.03–7.71 (m,
overlapping with the solvent signal, C6H4 + C6H5); 31P{1H} NMR
(CDCl3) d (ppm): À16.4 (br. s, 2P, PPh2), 27.6 (s, 1P, P@O), 55.0 (s,
1P, P@S). Anal. Calc. for C45H57CuN2O5P4S2 (957.52): C, 56.45; H,
6.00; N, 2.93. Found: C, 56.38; H, 6.08; N, 2.90%.
1009 (POC), 1534 (SCN), 3397 (NH). 1H NMR (CDCl3) d (ppm):
1.03–1.35 (m, 24H, CH3, iPr), 1.74 (br. s, 4H, CH2), 2.34 (br. s, 8H,
CH2), 3.28 (br. s, 4H, CH2N), 4.68 (br. s, 4H, OCH), 6.83–7.71 (m,
overlapped with the solvent signal, NH + Ph); 31P{1H} NMR (CDCl3)
d (ppm): À19.6 (br. s, 4P, PPh2), 56.0 (s, 2P, NPS). Anal. Calc. for
C70H86Cu2N4O4P6S4 (1488.65): C, 56.48; H, 5.82; N, 3.76. Found:
C, 56.32; H, 5.75; N, 3.80%.
5: Yield 0.434 g (79%), mp 93–94 °C. IR
m
(cmÀ1): 607 (P@S),
1011 (POC), 1198 (P@O), 1558 (SCN), 3276 (NH). 1H NMR (CDCl3)
10: Yield 0.610 g (68%), mp 142–143 °C. IR m
(cmÀ1): 614 (P@S),
d
(ppm): 0.98–1.22 (m, 18H, CH3, EtO + iPrO), 3.15 (d,
1012 (POC), 1527 (SCN), 3373 (NH). 1H NMR (CDCl3) d (ppm):
0.81–0.93 (m, 24H, CH3, iPr), 3.19 (br. s, 4H, CH2N), 4.21 (br. s,
8H, C5H4), 4.29 (br. s, 8H, C5H4), 4.46–4.91 (m, 8H, OCH + CH2N),
7.16–7.48 (m, overlapped with the solvent signal, NH + Ph);
31P{1H} NMR (CDCl3) d (ppm): À17.9 (br. s, 4P, PPh2), 56.2 (s, 2P,
NPS). Anal. Calc. for C84H90Cu2Fe2N4O4P6S4 (1772.53): C, 56.92; H,
5.12; N, 3.16. Found: C, 56.81; H, 5.18; N, 3.22%.
2JP,H = 20.9 Hz, 2H, CH2, P(O)CH2), 3.77–4.06 (m, 4H, OCH2, EtO),
4.24 (br. s, 4H, C5H4), 4.29 (br. s, 4H, C5H4), 4.62 (d. sept,
3JH,H = 6.1 Hz, JPOCH = 9.3 Hz, 2H, OCH, iPrO), 6.89 (s, 1H, NH),
3
7.23–8.11 (m, overlapping with the solvent signal, C6H4 + C6H5);
31P{1H} NMR (CDCl3) d (ppm): À16.9 (br. s, 2P, PPh2), 27.2 (s, 1P,
P@O), 54.8 (s, 1P, P@S). Anal. Calc. for
C52H59CuFeN2O5P4S2
(1099.46): C, 56.81; H, 5.41; N, 2.55. Found: C, 56.92; H, 5.36; N,
2.51%.
3.4. Synthesis of 11–14
3.2. Synthesis of 6
A suspension of H4LIII (0.116 g, 0.1 mmol) in 96% aqueous etha-
nol (10 mL) was mixed with an 96% ethanol solution of potassium
A suspension of H2LII (0.269 g, 0.5 mmol) in ethanol (35 mL)
hydroxide (0.025 g, 0.44 mmol).
A mixture of CuI (0.076 g,
was mixed with an ethanol solution of potassium hydroxide
0.4 mmol) and Ph2P(CH2)nPPh2 (n = 1, 0.154 g; n = 2, 0.159 g;

64
D.A. Safin et al. / Inorganica Chimica Acta 370 (2011) 59–64
n = 3, 0.165 g; 0.4 mmol) or Ph2P(C5H4FeC5H4)PPh2 (0.222 g,
0.4 mmol) in CH2Cl2 (10 mL) was refluxed for 5 min and then
added dropwise under vigorous stirring to the resulting potassium
salt. The mixture was stirred for an hour and the resulting precip-
itate of KI was filtered off. The filtrate was concentrated until crys-
tallization began. Isolated solid materials were obtained from a
dichloromethane/n-hexane mixture 1:5 (v/v).
The complexes 2–5 and 7–14 exhibit emission in the solid state
at ambient temperature. Furthermore, the complexes 2 and 11
exhibits marked long-wavelength emission in the solid state under
the same conditions.
References
11: Yield 0.186 g (71%), mp 193–194 °C. IR m
(cmÀ1): 642 (P@S),
[1] For examples see: (a) M. Pellei, C. Pettinari, C. Santini, B.W. Skelton, N. Somers,
A.H. White, J. Chem. Soc., Dalton Trans. (2000) 3416;
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White, J. Chem. Soc., Dalton Trans. (2002) 2333;
1013 (POC), 1558 (SCN). 1H NMR (DMSO-d6) d (ppm): 1.31 (d,
3JH,H = 6.0 Hz, 48 H, CH3, iPr), 1.52–4.48 (m, 36 H, CH2), 4.76 (d. sept,
3
3JH,H = 6.2 Hz, JP,H = 9.7 Hz, 8 H, OCH), 6.74–8.11 (m, 160 H, Ph);
(c) G.A. Bowmaker, S.E. Boyd, J.V. Hanna, R.D. Hart, P.C. Healy, B.W. Skelton,
A.H. White, J. Chem. Soc., Dalton Trans. (2002) 2722;
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(e) P. Aslanidis, P.J. Cox, S. Divanidis, A.C. Tsipis, Inorg. Chem. 41 (2002) 6875;
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(i) P. Aslanidis, P.J. Cox, A. Kaltzoglou, A.C. Tsipis, Eur. J. Inorg. Chem. (2006)
334;
(j) C. Pettinari, C. di Nicola, F. Marchetti, R. Pettinari, B.W. Skelton, N. Somers,
A.H. White, W.T. Robinson, M.R. Chierotti, R. Gobetto, C. Nervi, Eur. J. Inorg.
Chem. (2008) 1974.;
31P{1H} NMR (DMSO-d6) d (ppm): À26.9 to À11.4 (m, 16 P, PPh2),
51.4 (s, 4 P, NPS). Anal. Calc. for C238H256Cu8I4N8O8P20S8 (5248.64):
C, 54.46; H, 4.92; N, 2.13. Found: C, 54.68; H, 5.03; N, 2.07%.
12: Yield 0.252 g (84%), mp 96–97 °C. IR m
(cmÀ1): 623 (P@S),
1008 (POC), 1517 (SCN). 1H NMR (CDCl3) d (ppm): 1.17–1.29 (m,
48 H, CH3, iPr), 1.46–4.31 (m, 36 H, CH2), 4.84 (d. sept,
3
3JH,H = 6.1 Hz, JP,H = 10.2 Hz, 8 H, OCH), 6.91–7.72 (m, overlapped
with the solvent signal, Ph); 31P{1H} NMR (CDCl3) d (ppm): À13.8
(br. s, 8 P, PPh2), 50.7 (s, 4 P, NPS). Anal. Calc. for C142H172Cu4-
N8O8P12S8 (3001.33): C, 56.83; H, 5.78; N, 3.73. Found: C, 56.68;
H, 5.82; N, 3.68%.
13: Yield 0.223 g (73%), mp 118–119 °C. IR m
(cmÀ1): 620 (P@S),
(k) P. Aslanidis, P.J. Cox, K. Kapetangiannis, A.C. Tsipis, Eur. J. Inorg. Chem.
(2008) 5029;
1012 (POC), 1528 (SCN). 1H NMR (CDCl3) d (ppm) 1.22 (d,
3JH,H = 6.0 Hz, 24 H, CH3, iPr), 1.29 (d, 3JH,H = 6.2 Hz, 24 H, CH3, iPr),
1.50–4.53 (m, 44 H, CH2), 4.69 (d. sept, 3JH,H = 6.0 Hz, 3JP,H = 10.1 Hz,
8 H, OCH), 7.14–8.06 (m, overlapped with the solvent signal, Ph);
31P{1H} NMR (CDCl3) d (ppm): –17.1 (br. s, 8 P, PPh2), 50.9 (s, 4 P,
NPS). Anal. Calc. for C146H180Cu4N8O8P12S8 (3057.43): C, 57.36; H,
5.93; N, 3.66. Found: C, 57.42; H, 5.98; N, 3.74%.
(l) R.J. Bowen, M. Navarro, A.-M.J. Shearwood, P.C. Healy, B.W. Skelton, A.
Filipovska, S.J. Berners-Price, Dalton Trans. (2009) 10861;
(m) M. Sircoglou, S. Bontemps, M. Mercy, K. Miqueu, S. Ladeira, N. Saffon, L.
Maron, G. Bouhadir, D. Bourissou, Inorg. Chem. 49 (2010) 3983.
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Chim. Acta 357 (2004) 1063;
(b) P. Aslanidis, P.J. Cox, S. Divanidis, P. Karagiannidis, Inorg. Chim. Acta 357
(2004) 4231;
(c) S. Divanidis, P.J. Cox, P. Karagiannidis, P. Aslanidis, Polyhedron 24 (2005)
351;
14: Yield 0.334 g (92%), mp 153–154 °C. IR m
(cmÀ1): 618 (P@S),
1004 (POC), 1524 (SCN). 1H NMR (CDCl3) d (ppm): 1.08–1.34 (m, 48
H, CH3, iPr), 1.67–4.59 (m, 42 H, CH2 + C5H4), 4.69 (d. sept,
(d) A. Kaltzoglou, P.J. Cox, P. Aslanidis, Inorg. Chim. Acta 358 (2005) 3048;
(e) P.J. Cox, A. Kaltzoglou, P. Aslanidis, Inorg. Chim. Acta 359 (2006) 3183;
(f) M. Mamais, P.J. Cox, P. Aslanidis, Polyhedron 27 (2008) 175;
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[3] V.W.-W. Yam, K.K.-W. Lo, C.-R. Wang, K.-K. Cheung, J. Phys. Chem. A 101
(1997) 4666.
3
3JH,H = 6.1 Hz, JP,H = 10.9 Hz, 8 H, OCH), 7.19–7.94 (m, overlapped
with the solvent signal, Ph); 31P{1H} NMR (CDCl3) d (ppm): À20.7
(br. s, 8 P, PPh2), 51.1 (s, 4 P, NPS). Anal. Calc. for C174H188Cu4Fe4-
N8O8P12S8 (3625.19): C, 57.65; H, 5.23; N, 3.09. Found: C, 57.41;
H, 5.27; N, 3.14%.
[4] (a) N.G. Zabirov, A.Yu. Verat, F.D. Sokolov, M.G. Babashkina, D.B. Krivolapov,
V.V. Brusko, Mendeleev Commun. 13 (2003) 163;
(b) A.Y. Verat, F.D. Sokolov, N.G. Zabirov, M.G. Babashkina, D.B. Krivolapov, V.V.
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(c) F.D. Sokolov, M.G. Babashkina, D.A. Safin, A.I. Rakhmatullin, F. Fayon, N.G.
Zabirov, M. Bolte, V.V. Brusko, J. Galezowska, H. Kozlowski, Dalton Trans.
(2007) 4693;
3.5. Physical measurements
Infrared spectra (Nujol) were recorded with a Bruker IFS66
m
S
(d) D.A. Safin, M.G. Babashkina, T.R. Gimadiev, M. Bolte, M.V. Pinus, D.B.
Krivolapov, I.A. Litvinov, Polyhedron 27 (2008) 2978;
(e) M.G. Babashkina, D.A. Safin, Ł. Szyrwiel, M. Kubiak, F.D. Sokolov, Y.V.
Starikov, H. Kozlowski, Z. Anorg. Allg. Chem. 635 (2009) 554;
(f) R.C. Luckay, X. Sheng, C.E. Strasser, H.G. Raubenheimer, D.A. Safin, M.G.
Babashkina, A. Klein, Dalton Trans. (2009) 4646;
(g) D.A. Safin, M.G. Babashkina, M. Bolte, F.D. Sokolov, V.V. Brusko, Inorg. Chim.
Acta 362 (2009) 1895;
(h) F.D. Sokolov, M.G. Babashkina, F. Fayon, A.I. Rakhmatullin, D.A. Safin, T.
Pape, F.E. Hahn, J. Organomet. Chem. 694 (2009) 167;
(i) D.A. Safin, M.G. Babashkina, M. Bolte, A. Klein, CrystEngComm 12 (2010)
134;
spectrometer in the range 400–3600 cmÀ1. NMR spectra were ob-
tained on a Bruker Avance 300 MHz spectrometer at 25 °C. 1H
and 31P{1H} NMR spectra were recorded at 299.948 and
121.420 MHz, respectively. Chemical shifts are reported with refer-
ence to SiMe4 (1H) and 85% H3PO4
surements were carried out on
(
a
31P{1H}). Fluorescence mea-
FL 3-221-NIR Jobin Jvon
spectrofluorometer at room temperature. Elemental analyses were
performed on a CHNS HEKAtech EuroEA 3000 analyzer.
(j) M.G. Babashkina, D.A. Safin, A. Klein, M. Bolte, Eur. J. Inorg. Chem. (2010)
4018.
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Kozlowski, Polyhedron 26 (2007) 1113.
4. Conclusions
In summary, the reaction of [Cu(PPh3)3I] or a mixture of CuI and
Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 with the potassium
salts of HLI, H2LII or H4LIII has allowed us to obtain complexes 1–
14. The formation of the complexes 2, 7 and 11 is favored by the
small bite angle of the Ph2PCH2PPh2 diphosphane. The complex 1
forms dimers in the crystal by the NH function and the oxygen
atom of the phosphoryl P@O group.
[6] B. König, M. Pelka, M. Subat, I. Dix, P.G. Jones, Eur. J. Org. Chem. 10 (2001) 1943.
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