Synthesis, structure and spectroscopic properties of bis(triphenylphosphane)iminium (chlorido)(cyanido)argentates(I)

Article abstract of DOI:10.1016/j.ica.2015.12.018

Four new compounds containing the (chlorido)_(2-x)(cyanido)_xargentate(I) anion (x = 2, 1.63, 1 and 0.5) are reported. Their solid-state structures with the monocation PPN, bis(triphenylphosphane)iminium, are described; in a few cases the products also contain solvent molecules. The compounds have the formula (PPN)₂[Ag₂Cl₃(CN)], (PPN)[Ag(CN)Cl](CH₂Cl₂) and (PPN)[Ag(CN)_1.63Cl_0.37](hexane)_0.5 and (PPN)[Ag(CN)₂](CH₂Cl₂). Apart from the molecular structures and the synthetic process, also the solid-state luminescence has been studied. In the case of (PPN)₂[Ag₂Cl₃(CN)], the silver ions are pseudo-trigonally coordinated, with 2 chloride bridges between the Ag⁺ ions. The terminal Cl^- and terminal CN^- ligands are disordered over two positions, but only a single ¹³C NMR signal is observed for the cyanide ligands of this compound. The compound (PPN)[Ag(CN)₂] serves as a reference compound and contains the linear [Ag(CN)₂] unit. The compound with CN/Cl = 1.0 shows disorder of the [AgCl(CN)] unit, and also in the compounds with other CN/Cl ratios, disorder among the Cl^- and CN^- ligands is seen. The Ag⁺ ion is linearly coordinated by two ligands in these two cases, and for cyanides normal Ag-C bond lengths are observed in both cases (1.97-1.99 ?). The [Ag(CN)₂] anion is linear and uneventful. The PPN cation has normal bond lengths in all 4 compounds and no short contacts with other atoms in the lattice are observed. The luminescence properties of the new compounds were explored as solid powders. Only one of the compounds (compound 2, with x = 1) shows luminescence under excitation. The other three compounds do not show emission when irradiated at 320 nm, 350 nm or 380 nm.

Full text of DOI:10.1016/j.ica.2015.12.018

Inorganica Chimica Acta 443 (2016) 45–50
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Synthesis, structure and spectroscopic properties of
bis(triphenylphosphane)iminium (chlorido)(cyanido)argentates(I)
Mohammed Jaafar a, Xue Liu b, Fabian Dielmann c, F. Ekkehardt Hahn c, Khalid Al-Farhan a, Ali Alsalme a,
Jan Reedijk a,b,
⇑
a Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Kingdom of Saudi Arabia
b Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands
c Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 30, D-48149 Münster, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Four new compounds containing the (chlorido)(2ꢀx)(cyanido)xargentate(I) anion (x = 2, 1.63, 1 and 0.5) are
reported. Their solid-state structures with the monocation PPN, bis(triphenylphosphane)iminium, are
described; in a few cases the products also contain solvent molecules. The compounds have the formula
(PPN)2[Ag2Cl3(CN)], (PPN)[Ag(CN)Cl](CH2Cl2) and (PPN)[Ag(CN)1.63Cl0.37](hexane)0.5 and (PPN)[Ag(CN)2]
(CH2Cl2). Apart from the molecular structures and the synthetic process, also the solid-state lumines-
cence has been studied.
In the case of (PPN)2[Ag2Cl3(CN)], the silver ions are pseudo-trigonally coordinated, with 2 chloride
bridges between the Ag+ ions. The terminal Clꢀ and terminal CNꢀ ligands are disordered over two posi-
tions, but only a single 13C NMR signal is observed for the cyanide ligands of this compound. The com-
pound (PPN)[Ag(CN)2] serves as a reference compound and contains the linear [Ag(CN)2] unit.
The compound with CN/Cl = 1.0 shows disorder of the [AgCl(CN)] unit, and also in the compounds with
other CN/Cl ratios, disorder among the Clꢀ and CNꢀ ligands is seen. The Ag+ ion is linearly coordinated by
two ligands in these two cases, and for cyanides normal Ag–C bond lengths are observed in both cases
(1.97–1.99 Å). The [Ag(CN)2] anion is linear and uneventful. The PPN cation has normal bond lengths
in all 4 compounds and no short contacts with other atoms in the lattice are observed. The luminescence
properties of the new compounds were explored as solid powders. Only one of the compounds (com-
pound 2, with x = 1) shows luminescence under excitation. The other three compounds do not show
emission when irradiated at 320 nm, 350 nm or 380 nm.
Received 27 September 2015
Received in revised form 12 December 2015
Accepted 18 December 2015
Available online 23 December 2015
Keywords:
Silver
Luminescence
Cyanide anions
Chloride
PPN cation
Argentate
Ó 2015 Elsevier B.V. All rights reserved.
1. Introduction
metals, Cd and lanthanides [2–9]. Remarkably, only very few struc-
tures of this linear anion in the free state are known [10–13], i.e.
The poor solubility of silver halides has been known for a very
long time, and this property is still in common use for the analyt-
ical determination of halides in so-called argentometry [1].
These insoluble silver salts can be dissolved in excesses of
strong ligands, like ammonia and cyanide. With excess cyanide
the [bis(cyanide)argentate(I)] monoanion, [Ag(CN)2]ꢀ is formed
in such cases. A large variety of compounds based on this linear
anion is known, in which the negative charge is compensated by
metal ions, and where the N atom, bridges to the other metal
ion. Examples reported in the last decade comprise transition
not bridging to another metal ion.
Quite surprisingly, the first steps in this dissolution process
have hardly beꢀen studied so far, and the mixed anionic species
[Ag(CN)xCl(2ꢀx)
]
are poorly known and only one structure has
been reported to the best of our knowledge, based on the recent
CSD [14]. We therefore undertook a search for the possibility to
isolate such species with different Cl/CN ratios, i.e. different values
for x in [Ag(CN)xCl(2ꢀx)]ꢀ, with x = 2 (reference compound), 1.6, 1.0
and 0.5. These species indeed appear to be rare in the literature,
and in fact only one species has been structurally characterized,
namely (Et4N)[Ag2(CN)2Cl], which has a 3D polymeric structure
[15].
⇑
Corresponding author at: Leiden Institute of Chemistry, Leiden University, P.O.
Box 9502, 2300 RA Leiden, The Netherlands. Tel.: +31 715274459; fax: +31
715274671.
For the synthesis and characterization of the compounds in the
system, we decided to use non-aqueous solvents, and the very
large, innocent cation PPN, bis(triphenylphosphane)iminium was
E-mail address: Reedijk@chem.leidenuniv.nl (J. Reedijk).
http://dx.doi.org/10.1016/j.ica.2015.12.018
0020-1693/Ó 2015 Elsevier B.V. All rights reserved.

46
M. Jaafar et al. / Inorganica Chimica Acta 443 (2016) 45–50
selected for charge compensation, and especially, to maximize the
chances for obtaining molecular, anionic species. The results of this
study are described below, and 3 new compounds are reported
together with their 3D structures. To introduce the Ag+ ion in a sol-
uble form, we used silver acetylides, available from our previous
study [16].
lected as KC2Ph (0.115 g, 82%), m.p: 250 °C. To the remaining clear
solution gradually hexane (35 ml) was added and a crystalline
material precipitated, which was filtered and dried for 3 h at
90 °C (95%, 0.713 g), m.p: 180 °C. The elemental analysis indicates
a partial loss of lattice methylene chloride according to the formula
(C37H30AgClN2P2)(CH2Cl2)0.35. Found (Calc.): C, 60.74 (60.82); H,
As some Ag compounds are luminescent, like many d10 coinage
metal compounds, we have also explored their emission properties
in relation to the electronic structure of the compounds [17–22]
and these spectra are also reported.
4.04 (4.20); N, 3.93 (3.80)%. FTIR: m
max cmꢀ1 (KBr disk) 1282,
1262 (s, P–N), 1114 (s, P–C), 2135 (m), 2117 (w, C„N stretch).
2.3. Synthesis of (PPN)[Ag(CN)xCl2ꢀx](hexane)0.5, 3 (x = 1.63)
Bis(triphenylphosphane)iminium chloride, (PPN)Cl (0.574 g,
1 mmol) was added to a solution of potassium cyanide, KCN
(0.065 g, 1 mmol) in methanol (30 mL). While stirring for 60 min
a clear solution was obtained, and subsequently, silver pheny-
lacetylide, [AgC2But]n (0.189 g, 1 mmol) was added and dissolved
during 15 min. After 30 min a white solid precipitated. The suspen-
sion was evaporated to dryness, and then the residue was
extracted with dichloromethane, CH2Cl2 (25 mL), after which an
off-white precipitate was formed. This was filtered off and col-
lected as KC2But (0.097 g, 80%), m.p: 220 °C. To the remaining clear
solution gradually hexane (35 ml) was added and a crystalline
material precipitated, which was filtered and dried in vacuo (95%,
0.713 g), m.p: 190 °C. A suitable crystal for XRD was obtained from
the same batch. This synthesis was performed repeatedly, and in
different batches slightly different analyses were found. The ele-
mental analyses were performed on a few samples. Found values
range (calculated using the formula found from the X-ray refine-
ment, C39.13H33.5AgCl0.37N2.63P2): C, 65.23–64.00 (64.97); H, 4.68–
2. Experimental part
Starting materials were used as purchased without further
purification. The salt bis(triphenylphosphane)iminium chloride,
(PPN)Cl, was used as commercially available (Aldrich; Analar
grade). Potassium cyanide was also used as commercially available
(Koch-Light Labs. Ltd grade). Hexane, methylene chloride, acetone
and methanol were used as commercially available (BDH-Analar
grade) and kept over molecular sieves. The Ag-acetylide intermedi-
ate products were prepared as reported before [16,23]. Synthesis of
(PPN)CN: Potassium cyanide, KCN (0.065 g, 1 mmol) was added to
a clear solution of bis(triphenylphosphane)iminium chloride, (PPN)
Cl (0.574 g, 1 mmol) in acetone (20 mL). After stirring for 20 min a
white solid precipitate was formed. The solid was filtered off and
collected as KCl, (0.074 g, 98%), m.p. > 3 °C. To the remaining clear
solution n-hexane (40 mL) was added, upon which a precipitate
was formed, which was finally collected as a solid with formula
(PPN)CN in high yield (99%, 0.56 g), m.p. 253 °C, FTIR:
m max
4.93 (4.67); N, 3.89–5.83 (5.09); FTIR:
1282, 1262 (s, P–N), 1114 (s, P–C), 2135 (m), 2117 (w, C„N
stretching).
m
max cmꢀ1 (KBr disk)
cmꢀ1 (KBr disk) 1293, 1242 (s, P–N), 1114 (s, P–C), 2214
(vw, C„N stretch).
2.1. Synthesis of (PPN)2[Ag2Cl3(CN)], 1
2.4. Synthesis of (PPN)[Ag(CN)2](CH2Cl2), 4
3,3-Dimethylbutynylsilver(I) [AgC2But]n (0.189 g, 1 mmol) was
added to a clear solution of bis(triphenylphosphane)iminium chlo-
ride, (PPN)Cl (0.574 g, 1 mmol) in methanol (30 mL). While stirring
for 30 min a clear solution was formed, and subsequently potas-
sium cyanide, KCN (0.065 g, 1 mmol), was added and dissolved
within 10 min. After 20 min a yellowish solid precipitated. The sus-
pension was evaporated to dryness, and then the residue was
extracted with dichloromethane, CH2Cl2 (25 mL). In a few minutes
a yellowish precipitate was formed, which was filtered off and col-
lected as K-C2But (0.070 g, 93%), m.p: 220 °C. To the remaining
clear solution, n-hexane (40 ml) was slowly added, resulting in a
off-white crystalline material, which was collected by filtration
and was isolated in high yield (90%, 0.774 g), m.p 203 °C. The crys-
tals were found suitable for XRD analysis. Elemental analysis,
according to the formula (C73H60Ag2Cl3N3P4): Found (Calc.): C,
Silver cyanide [Ag(CN)]n (0.134 g, 1 mmol) was added to a solu-
tion of KCN (0.065 g, 1 mmol) in methanol (40 ml) according to Al-
Ohaly [24]. After a clear solution had been obtained, (PPN)Cl
(0.574 g, 1 mmol) was gradually added to the reaction mixture.
Stirring was continued for 15 min. The solution was evaporated
to dryness and the white residue was treated with methylene chlo-
ride (30 ml). The insoluble KCl (0.065 g) was filtered off. Addition
of hexane to the filtrate gave white crystals which were isolated
by filtration and dried at 100 °C for 3 h (0.663 g, 95%), m.p.:
188 °C. The elemental analysis indicates a partial loss of lattice
methylene chloride according to the formula (C38H30AgN3P2)(CH2-
Cl2)0.2 Found (Calc.): C, 65.78 (64.13); H, 4.46 (4.28); N, 5.58
(5.87)%. FTIR: max
(s, P–C), 2137 (s), C„N stretching).
m
cmꢀ1 (KBr disk) 1286, 1266 (s, P–N), 1114
Single crystals of compounds 1–4 were collected from the syn-
thetic batches. A suitable crystal for an X-ray structure analysis
was selected for each case and measured on a Bruker APEX-II
CCD diffractometer. Each crystal was kept at 153.2 K during data
collection. Using OLEX2 [25] the structures were solved with the
Superflip [26–28] structure solution program by Charge Flipping
and refined with the SHELXL [29] refinement package, using Least
Squares minimization. Structural data are listed in Table 1.
All elemental analyses were performed by using a Perkin Elmer
Series II-2400 analyzer and the FT-IR spectra were recorded on a
Thermo Scientific Nicolet iS10. NMR spectra (proton and 13C) were
recorded on a JEOL ECP-400 NMR in CDCl3.
The excitation and emission spectra were recorded at room
temperature using a Shimadzu RF-5301PC spectrofluorophotome-
ter equipped with a solid-state sample holder. The excitation spec-
trum was recorded by constantly monitoring the emission
spectrum at the wavelength of most intense luminescence while
61.84 (61.50); H, 4.04 (4.21); N, 3.15 (2.95)%; FTIR:
m
max cmꢀ1
(KBr disk) 1283, 1261(s, P–N), 1114 (s, P–C), 2137 (m, C„N
stretch). 13C NMR (at 25 °C in dmso, at 400 MHz): single CN signal
at 206.28 ppm.
2.2. Synthesis of (PPN)[Ag(CN)Cl](CH2Cl2), 2
Bis(triphenylphosphane)iminium chloride, (PPN)Cl (0.574 g,
1 mmol) was added to a clear solution of potassium cyanide, KCN
(0.065 g, 1 mmol) in methanol (30 mL). While stirring for 60 min
a clear solution was obtained, and subsequently, silver pheny-
lacetylide, [AgC2Ph]n (0.209 g, 1 mmol) was added and dissolved
during 15 min. After 30 min a white solid precipitated. The suspen-
sion was evaporated to dryness, and then the residue was
extracted with dichloromethane, CH2Cl2 (25 mL), after which an
off-white precipitate was formed. This was filtered off and col-

Table 1
Crystal data and structure refinement for compounds 1 - 4.
Sample code
1
2
3
4
CCDC number
Empirical formula
Formula weight
T (K)
1418113
1418114
C38H32AgCl3N2P2
792.81
1418115
C39.13H33.5AgCl0.37N2.63P2
723.49
1418116
C39H32AgCl2N3P2
783.38
C
73H60Ag2Cl3N3P4
1425.21
153(1)
153(1)
153(1)
153(1)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
orthorhombic
Pbca
19.4166(4)
15.9075(3)
20.2452(4)
90
monoclinic
P21/c
9.1475(4)
23.8402(10)
16.7950(7)
90
monoclinic
P21/c
9.1083(2)
23.8769(5)
17.0069(4)
90
monoclinic
P21/c
9.1170(7)
23.9562(18)
16.9256(13)
90
a
(°)
b (°)
90
90
6253.1(2)
4
1.514
101.560(2)
90
3588.3(3)
4
1.468
0.904
100.8150(10)
90
3632.93(14)
4
1.323
0.700
100.9935(17)
90
3628.9(5)
4
1.434
0.823
c
(°)
V (Å3)
Z
Dcalc (mg/mm3)
Absorption coefficient (mmꢀ1
F(000)
)
0.904
2896.0
1608.0
1480.0
1592.0
Crystal size (mm3)
Radiation
0.61 ꢁ 0.32 ꢁ 0.22
0.27 ꢁ 0.14 ꢁ 0.14
0.40 ꢁ 0.28 ꢁ 0.20
0.33 ꢁ 0.27 ꢁ 0.18
Mo K
a
(k = 0.71073)
Mo K
a
(k = 0.71073)
Mo Ka
(k = 0.71073)
Mo Ka (k = 0.71073)
2
H
range for data collection (°)
5.21–61.088
3.008–61.284
5.69–61.07
4.192–52.772
Index ranges
ꢀ27 6 h 6 27, ꢀ22 6 k 6 22, ꢀ28 6 l 6 28
ꢀ12 6 h 6 12, ꢀ32 6 k 6 34, ꢀ23 6 l 6 24
ꢀ13 6 h 6 13, ꢀ34 6 k 6 34, ꢀ24 6 l 6 24
ꢀ11 6 h 6 11, ꢀ29 6 k 6 29, ꢀ21 6 l 6 21
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit (GOF) on F2
109138
42560
64849
25613
9554 [Rint = 0.0363, Rsigma = 0.0186]
9554/0/406
1.120
10954 [Rint = 0.0266, Rsigma = 0.0241]
10954/0/451
1.023
11081 [Rint = 0.0375, Rsigma = 0.0277]
11081/0/443
1.138
7355 [Rint = 0.0288, Rsigma = 0.0279]
7355/0/417
1.065
Final R indexes [I P 2
r
(I)]
R1 = 0.0286, wR2 = 0.0833
R1 = 0.0331, wR2 = 0.0858
0.43/ꢀ0.37
R1 = 0.0400, wR2 = 0.1104
R1 = 0.0487, wR2 = 0.1158
1.05/ꢀ1.28
R1 = 0.0489, wR2 = 0.1389
R1 = 0.0544, wR2 = 0.1425
1.59/ꢀ1.05
R1 = 0.0560, wR2 = 0.1491
R1 = 0.0658, wR2 = 0.1562
1.38/ꢀ1.50
Final R indexes (all data)
Largest diff. peak/hole [e Åꢀ3
]

48
M. Jaafar et al. / Inorganica Chimica Acta 443 (2016) 45–50
Fig. 1. Room temperature excitation (left) and emission (right) spectra of compound 2. Details are presented in the inset.
scanning the excitation wavelength from 220 to 400 nm. The exci-
tation spectrum has been corrected for the response of the detector
and light source.
3. Results and discussion
3.1. Synthesis, characterization and luminescence
Some of the new compounds appeared to crystallize with lattice
solvents, filling up the pores in the lattice, i.e. hexane for com-
pound 3, and methylene chloride for compound 2. All compounds
can be described by the general formula: [PPN][AgCl2ꢀx(CN)x] (1:
x = 0.5, 2: x = 1, 3: x = 1.63, 4: x = 2). In addition to elemental anal-
yses, see experimental part, the compounds were also investigated
by IR spectroscopy. All expected bands for the CN ligand and for
PPN bands were observed, and in particular the C„N triple bond,
near 2100 cmꢀ1, is a prominent structural marker. For compound
1 also a 13C NMR spectrum was recorded to be sure that, given
the disordered X-ray structure, only one chemically distinct CN
anion was present. The single, sharp resonance peak at
206.9 ppm indeed shows that this is the case.
The emission and excitation spectra of compounds 1–4 (few
batches for each) were studied in the solid state and compared
with earlier data from our laboratory on related compounds [30–
32]. It appears that only a nice, blue intense luminescence is
observed for compound 2, (see Fig. 1) which is comparable to that
of related heteronuclear (cyanido)silver compounds [30–32]. Most
remarkable, compounds 1, 3 and 4 do not show any luminescent
behavior, under the excitation of 320 nm, 350 nm and 380 nm.
For reference purposes, we therefore have also measured the lumi-
nescence of the known compound [PPN]Cl, this compound also
shows no luminescence. Packing effects, to be discussed below,
are therefore the most likely origins for the unique luminescence
of compound 2.
Fig. 2. Projection of cation, anion and lattice solvent molecules in compound 1 with
thermal ellipsoid plot at the 50% levels of probability. Only one component (50%
occupancy) of the disordered part is depicted. Selected bond lengths [Å] and angles
[°] for the metal species are: Ag1a–Cl2 2.625(3), Ag1a–Cl20 2.509(2), Ag1a–C1 2.033
(7), Ag1b0–Cl10 2.448(3), Ag1b0–Cl20 2.766(3), Ag1b0–Cl2 2.419(2), C1–N1 1.133(6),
Ag1a–Cl2–Ag1b0 85.57(8), Ag1a–Cl20–Ag1b0 80.94(8), Cl2–Ag1a–Cl20 97.46(8), Cl2–
Ag1b0–Cl20 95.98(8), Cl2–Ag1b0–Cl10 150.36(13), Cl20–Ag1b0–Cl10 113.66(11).

M. Jaafar et al. / Inorganica Chimica Acta 443 (2016) 45–50
49
Fig. 3. Projection of cation, anion and lattice solvent molecules in compound 2 with thermal ellipsoid plot at the 50% levels of probability. Only the main component (65%
occupancy) of the disordered part is depicted. The large thermal ellipsoid for CH2Cl2 agree with partial occupancy. Selected bond lengths [Å] and angles [°] for the metal
species are: Ag1a–Cl1a 2.3286(19), Ag1a–C1a 2.040(7), C1a–N1a 1.231(14), Cl1a–Ag1a–C1a 178.9(3), Ag1a–C1a–N1a 178.1(11).
3.2. Crystal structure descriptions
oclinic space group P21/c with very similar lattice constants. The
same packing of the PPN+ cation and the [AgL2]ꢀ anion is observed
with some dichloromethane (2, 4; 0.5 and 0.2 per Ag, resp. from
elemental analysis, but refined as 1.0), or 0.5 n-hexane (3) captured
in the crystal lattice (cf. Supporting Information). There are no
close contacts between the cation and the anion. A projection of
the asymmetric unit displaying the main component of compound
2 is given in Fig. 3, together with selected geometric details. Other
relevant bond lengths and distances are given in the SI, Tables S3
and S4. Fig. 4 shows a projection of compound 3, with relevant
details in the caption together with selected geometric details.
Other relevant bond lengths and distances are given in Tables S5
and S6.
Compound 1, in which has the value x = 0.5, contains a dinu-
clear anion, with trigonally coordinated Ag(I) ions; one of the silver
ions is coordinated by 3 chlorides, two of which are bridging,
whereas the other silver ion binds to a cyanide as the terminal
ligand. In the crystal lattice they are disordered over 2 positions
in 50/50 ratio (cf. Fig. S2), but only a single 13C NMR signal is
observed for the cyanide ligand of this compound. The relevant
Ag–L distances are given in the figure caption below. There are
no close contacts between the cation and the anion in compound
1. The intramolecular bonds for the PPN cation are uneventful.
A projection of compound 1 is presented in Fig. 2, together with
selected geometric details. Other relevant bond lengths and dis-
tances are given in the Tables S1 and S2.
The structure of the bis(cyanido)argentate compound is pre-
sented in Fig. 5. In this case the [Ag(CN)2] unit is not disordered
and has a linear structure as expected. Selected geometric details
are given in the caption. Other relevant bond lengths and distances
are given in the Tables S7 and S8.
Compounds 2 (x = 1), 3 (x = 1.63) and 4 (x = 2) each contain a
linear coordinated Ag(I) ion, by cyanide and chloride, albeit over
disorder positions for x < 2. Compounds 2–4 crystallize in the mon-
Fig. 4. Projection of cation and anion in compound 3 (x = 1.63) with thermal ellipsoid plot at the 50% levels of probability. Only the main component (63% occupancy) of the
disordered part is depicted. The partially occupied hexane solvent molecule in the crystal lattice is omitted. Selected bond lengths [Å] and angles [°] for the metal species are:
Ag1–C1 2.005(5), Ag1–C2 1.947(7), C1–N1 1.177(5), C2–N2 1.179(8), C1–Ag1–C2 178.6(3).

50
M. Jaafar et al. / Inorganica Chimica Acta 443 (2016) 45–50
Appendix A. Supplementary material
CCDC 1418113–141116 contain the supplementary crystallo-
graphic data for compounds 1, 2, 3 and 4. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary
data associated with this article can be found, in the online version,
at http://dx.doi.org/10.1016/j.ica.2015.12.018.
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Fig. 5. Projection of cation and anion in compound 4 (x = 2) with thermal ellipsoid
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Packing in all compounds appears as uneventful, without signif-
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Figs. S8–S11. Careful analyses of the intermolecular contacts can-
not explain the fact that only compound
luminescence.
2 shows blue
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The results presented above have shown that the chloride ions
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tallized. The large bis(triphenylphosphane)iminium counter
cation, PPN, remains innocent in the formed compounds and dis-
plays no short intermolecular contacts in the solid state. Open
spaces in the lattice are filled with CH2Cl2 or n-hexane.
The luminescence differences between the compounds are sur-
prising as only compound 2, having the Cl/CN ratio 1.0, displays
emission, where the other compounds do not, as observed from
several samples. Perhaps a quenching in the lattice by the PPN
and presence or absence of solvent may play a role, although inter-
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Acknowledgements
The Distinguished Scientist Fellowship Program (DSFP) at KSU
is gratefully acknowledged for supporting this project. Thanks are
due to the Chemical Industry Fund for a Liebig Fellowship (F.D.).