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Journal of Luminescence 186 (2017) 127–134

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Luminescence properties of copper(I), zinc(II) and cadmium(II)


coordination compounds with picoline ligands
Jan Grzegorz Małecki n, Anna Maroń
Department of Crystallography, Institute of Chemistry, University of Silesia, 9th Szkolna St., 40-006 Katowice, Poland

art ic l e i nf o a b s t r a c t

Article history: Mononuclear coordination compounds of copper(I) – [Cu(PPh3)2(picoline)(NO3)], zinc(II) –


Received 7 October 2016 [ZnCl2(picoline)2] (picoline ¼ 3– and 4–methylpyridine) and polymeric cadmium(II) – [CdCl2(β-
Received in revised form picoline)2]n were prepared and their luminescence properties in solid state and acetonitrile solutions
3 February 2017
were determined. Single crystal X-ray crystallography revealed distorted tetrahedral geometry around
Accepted 10 February 2017
Available online 11 February 2017
the central ions of the compounds. The compounds exhibit green photoluminescence in solid state and in
acetonitrile solutions. The emission of copper(I) compounds originated from metal-to-ligand charge
Keywords: transfer state combined with nitrato-to-picoline charge transfer state i.e. (1(M þX)LCT). The presence of
Copper(I) zinc(II) and cadmium(II) co- nitrato ligand in the coordination sphere of copper(I) compounds quenches the emission. Luminescence
ordination compounds
of zinc(II) and cadmium(II) compounds results from chloride-to-picoline charge transfer state and the
Picolines
quantum efficiency in the case of the polymeric Cd(II) compound reaches 39%. The photoluminescence
Crystal structure
Luminescence quantum yields of the mononuclear zinc(II) compounds vary from 10 to 16% depending on the conditions
(solid state, solution).
& 2017 Elsevier B.V. All rights reserved.

1. Introduction low temperature glasses although some of them, especially poly-


meric cadmium compounds exhibit phosphorescence both in solid
The luminescence properties of metal d10 coordination com- state and in solutions.
pounds are known since the seventies of the last century [1,2]. Although emission of Cu(I) coordination compounds is gen-
Thereafter work in the area of luminescent d10 metal coordination erally weak and short-lived there is a group of them showing in-
compounds has been developing rapidly. The coordination com- teresting luminescence properties. Polynuclear coordination
pounds of divalent zinc and cadmium as well as copper(I) exhibit compounds of copper(I) exhibit room-temperature phosphores-
very interesting photophysical properties. Obviously their lumi- cence [13–17] but also are known mononuclear phosphorescent Cu
nescent properties are dependent on the ligands in the coordina- (I) compounds [18–20]. The emission wavelength of these com-
tion sphere. Generally organic ligands derived from nitrogen het- pounds span the visible region of the spectrum and is located
erocyclic compounds can enhance or quench the emission. How- usually in the red due to the small energy gap between excited and
ever the coordination compounds may exhibit properties relevant ground states. However the metal-to-ligand charge transfer states,
for use them as photosensitisers or in OLEDs and “organic” light addicted to the ligand type, introduce the possibility of emission
emitting diodes (OLEDs) and light-emitting electrochemical cells wavelengths spanning the visible region. A particular role is played
by N-heteroaromatic ligands, which together with the tetragonal
(LEECs) [3]. An important problem is that many transition–metal
geometry of the coordination sphere of the compounds of metals
coordination compounds are based on the expensive metals such
such as copper, zinc and cadmium provide opportunities to obtain
as Ru(II), Pt(II), Re(I), Os(II) and Ir(III). Therefore not surprising that
the appropriate photophysic properties [21]. For example, simple
a significant extension of research dedicated to developing new
Cu(I) halide coordination compounds with 4-methylpyridine li-
photoactive coordination compounds of inexpensive elements
gand exhibit very strong blue fluorescence [22].
such as copper, zinc, cadmium. Nonetheless many zinc(II) and
In this paper we report the studies involving synthesis and
dinuclear and polymeric cadmium(II) diimine coordination com-
spectroscopic properties of the copper(I), zinc(II) and cadmium(II)
pounds exhibit intense fluorescence at ambient temperature [4–
coordination compounds with two picoline ligands i.e. 3-methyl–
12]. Phosphorescence of these compounds is usually observed in (β–pic) and 4-methylpyridine (γ–pic). The polymeric [CdCl2(β-
pic)2]n compound is known [23] but its photoluminescence
n
Corresponding author. properties have not yet been described. The γ-picoline analog was
E-mail address: gmalecki@us.edu.pl (J.G. Małecki). not studied due to the difficulty of obtaining a pure crystalline

http://dx.doi.org/10.1016/j.jlumin.2017.02.025
0022-2313/& 2017 Elsevier B.V. All rights reserved.
128 J.G. Małecki, A. Maroń / Journal of Luminescence 186 (2017) 127–134

product. In the reaction between cadmium(II) chloride and γ-pi- 292.2 (3.23), 268.0 (4.28), 262.6 (4.39), 257.4 (4.38); (solid state):
coline is formed immediately an insoluble white precipitate. In 351.7, 273.8, 230.1.
view of the effect of impurities on the emission properties the γ-
picoline analog of compound (5) has not been studied. As for the 2.3. Physical measurements
copper(I) coordination compounds with formula [Cu
(PPh3)2(picoline)X], in accordance with that stated above, the ha- Infrared spectra were recorded on a Nicolet iS5 FT-IR spectro-
lide complexes are very effective light emitters. Whereas our aim photometer in the spectral range 4000–400 cm-1 using KBr pellets.
was to determine the emission properties of the nitrato analogues. Elemental analyses (C, H, and N) were performed on a Perkin–El-
mer CHN-2400 analyzer. Electronic spectra were measured on the
Evolution 220 spectrophotometer in the range of 800–200 nm in
2. Experimental solid states. The NMR spectra were obtained with Bruker Avance
400 and 500 operating at 500.18 or 400.13 MHz (1H), 125.78 or
2.1. Materials and methods 100.5 MHz (13C), 202.47 or 162.0 MHz (31P) at 21 °C. Chemical
shifts referenced to ext. TMS (1H, 13C) or 85% H3PO4 (31P). Coupling
Cu(NO3)2.3H2O, ZnCl2.4H2O, CdCl2.2H2O, PPh3 and 3– and 4– constants are given in Hz.
methylpyridine were purchased from POCh Gliwice and Aldrich The steady-state and time-resolved emission spectra were
Chemical Co, respectively. The [Cu(PPh3)2NO3] coordination com- measured for solid states and EtOH:MeOH (4:1) solutions on the
pound was synthesized according to the literature method [23]. FLS-980 spectrophotometer at ambient temperature using a Xe
lamp as the light source and PMT as the detector. The Raman
2.2. General procedure for synthesis of coordination compounds scattering of solvents was always subtracted from the steady state
emission spectra of complexes. The fluorescence quantum yields
The copper(I) compounds were synthesized by a reaction be- were determined at room temperature, using the integrating
tween [Cu(PPh3)3NO3] (0.3 g, 5  10–4 mol) and an equimolar sphere with solvent as a blank. The solutions of samples were first
quantity of the β– or γ–picoline dissolved in methanol (50 cm3). filtered and diluted to absorbance under 0.1 to avoid inner filter
Zinc(II) and cadmium(II) compounds were synthesized by a reac- effects and influences of impurities from the medium. They were
tion between the solvated metal chlorides and picolines in a 1:2 then irradiated at the excitation wavelength of the coordination
stoichiometric ratio. The mixtures were refluxed for an hour. After compounds. Time-resolved measurements were made on optically
this time, they were cooled and filtered. Crystals suitable for X-ray diluted (0.05 oO.D o0.1) methanol:ethanol solutions at room
crystal analysis were obtained by slow evaporation of the reaction temperature using time-correlated single photon counting meth-
mixtures. ods. Additionally the emission properties were measured at the
[Cu(β-pic)(PPh3)2(NO3)] (1): Yield 72%. Anal. Calc. for low temperature (77 K) in MeOH:EtOH (1:4) frozen glasses. The
C47H38CuNO3P2: C 71.43% H 4.85% N 1.77%; Found: C 71.31% H excitation wavelength (340 nm) was obtained using a TCSPC diode
4.97% N 1.62%. IR (KBr): 3053, 3006, 2926 (νCH), 1586 (νC ¼ N), 1481 light source with a 100 ns pulse period and the PMT as the de-
(νCC); 1093 ν(P-CPh). UV–vis (CH3CN) [nm (ε)]: 259.2 (0.372); (so- tector. The system was aligned and the IRF was designated using a
lid): 459.2 (0.144), 375.4 (0.544), 314.2 (0.986), 277.7 (0.964), 233.0 ludox solution as a standard.
(0.795). 1H NMR (400 MHz, CDCl3) δ 8.68 (s), 7.83 (s), 7.82 (d,
J ¼7.7 Hz), 7.52 (d, J ¼20.5 Hz), 7.35 (d, J ¼50.9 Hz, 33 H), 2.47 (d, 2.4. Crystallography
J ¼19.5 Hz). 31P{1H} NMR (162 MHz, CDCl3) δ  1.33 (s). UV–vis
(acetonitrile) [nm] (logε): 259.2 (4.57); (solid state): 459.2, 375.4, The yellow crystals of compounds (1)–(5) were mounted in
314.2, 277.7, 233.0. turn on a Gemini Ultra Oxford Diffraction automatic diffractometer
[Cu(γ-pic)(PPh3)2(NO3)] (2): Yield 81%. Anal. Calc. for equipped with a CCD detector. X-ray intensity data were collected
C47H38CuNO3P2: C 71.68% H 5.01% N 1.74%; Found: C 71.77% H with graphite monochromated MoKα radiation (λ ¼ 0.71073 Å) at
5.18% N 1.52%. IR (KBr): 3050, 3016, 2925 (νCH), 1576 (νC ¼ N), 1481 295(2) K, in the ω scan mode. Ewald sphere reflections were
(νCC); 1093 ν(P-CPh). UV–vis (solid) [nm]: 570, 425, 350, 260. 1H collected up to 2θ ¼50.10. Details concerning crystal data and re-
NMR (400 MHz, CDCl3) δ 8.32–8.06 (m), 7.87 (s), 7.63–7.14 (m), finement are gathered in Table 1. Lorentz, polarization and em-
2.49 (s), 2.33 (s). 13C NMR (101 MHz, CDCl3) δ 153.61 (s), 134.07 (s), pirical absorption correction using spherical harmonics im-
133.44 (d, J¼ 14.0 Hz), 133.12 (s), 129.66 (s), 128.45 (t, J ¼11.5 Hz), plemented in SCALE3 ABSPACK scaling algorithm [25] were ap-
123.09 (s), 115.81–115.61 (m), 17.61 (s). 31P{1H} NMR (162 MHz, plied. The structure was solved by the Patterson method and
CDCl3) δ 1.12 (s). UV–vis (acetonitrile) [nm] (logε): 355.3 (3.15), subsequently completed by the difference Fourier recycling. All the
261.1 (4.38); (solid state): 425.7, 362.0, 327.6, 268.6, 217.1. non-hydrogen atoms were refined anisotropically using the full-
[ZnCl2(β-pic)2] (3): Yield 95%. Anal. Calc. for C47H38CuNO3P2: C matrix, least-squares technique. The Olex2 [26] and SHELXS,
68.45% H 4.52% N 1.70%; Found: C 68.31% H 4.41% N 1.62%. IR SHELXL [27] programs were used for all the calculations. Atomic
(KBr): 3026, 2953, 2914, 2859 (νCH), 1612 (νC ¼ N;C ¼ C). 1H NMR scattering factors were incorporated in the computer programs.
(400 MHz, CDCl3) δ 8.68 (s), 7.83 (s), 7.82 (d, J ¼7.7 Hz), 7.52 (d,
J ¼20.5 Hz), 7.35 (d, J¼ 50.9 Hz), 2.47 (d, J ¼19.5 Hz). UV–vis 2.5. Computational methods
(acetonitrile) [nm] (logε): 425.2 (2.30), 349.0 (3.26), 296.1 (3.49),
268.0 (4.23), 262.7 (4.33), 255.3 (4.29); (solid state): 425.2, 334.0, The calculations were carried out using the Gaussian09 [28]
281.8, 235.9. program. Molecular geometries of the singlet ground state of the
[ZnCl2(γ-pic)2] (4): Yield 91%. Anal. Calc. for C47H38CuNO3P2: C compounds were fully optimized in the gas phase using the B3LYP
68.45% H 4.52% N 1.70%; Found: C 68.29% H 4.38% N 1.59%.IR (KBr): functional [29]. For each of the compounds a frequency calculation
3039, 2922 (νCH), 1627 (νC ¼ N). 1H NMR (400 MHz, CDCl3) δ 8.62 was carried out, verifying that the optimized molecular structure
(s), 7.88–6.79 (m), 7.09 (d, J ¼59.9 Hz), 2.46 (s). UV–vis (acetoni- corresponds to energy minimum, thus only positive frequencies
trile) [nm] (logε): 423.3 (2.60), 369.6 (3.04), 296.1 (3.18), 260.2 were expected. The lanl2dz (Los Alamos National Laboratory
(4.14), 254.0 (4.23); (solid state): 426.2, 326.4, 259.2, 215.5. 2 Double-Zeta) ECP [29] basis set was used to describe the metal
[CdCl2(β-pic)2]n (5): IR (KBr): 3026, 2957, 2925 (νCH), 1604 atoms and the basis set used for the lighter ones (C, N, O, Cl, P, H)
(νC ¼ N). UV–vis (acetonitrile) [nm] (logε): 426.2 (2.78), 368.4 (3.15), was 6–31 g with a set of ‘‘d” and ‘‘p” polarization functions.
J.G. Małecki, A. Maroń / Journal of Luminescence 186 (2017) 127–134 129

Table 1
Crystal data and structure refinement details of [Cu(PPh3)2(β-pic)NO3]] (1), [Cu(PPh3)2(γ-pic)NO3] (2), [Zn(β-pic)Cl2] (3), [Zn(γ-pic)Cl2] (4) and [Cd(β-pic)Cl2]n (5) coordination
compounds.

1 2 3 4 5

Empirical formula C42H37CuN2O3P2 C42H37CuN2O3P2 C12H14Cl2N2Zn C12H14Cl2N2Zn C12H14CdCl2N2


Formula weight 743.21 743.21 322.52 322.52 369.55
Temperature [K] 295(2) 295(2) 295(2) 295(2) 295(2)
Crystal system monoclinic triclinic orthorhombic monoclinic monoclinic
Space group P21/c P–1 Pbca P21/c P21/c

Unit cell dimensions


a [Å] 9.8646(5) 9.4216(7) 17.0115(10) 14.3361(10) 3.8685(4)
b [Å] 37.6198(13) 10.1762(7) 8.7037(5) 7.8919(5) 14.6467(17)
c [Å] 10.9178(6) 19.8053(7) 19.2603(15) 13.4939(9) 11.8962(14)
α [ο] 90 90.890(4) 90 90 90
[βο] 113.236(6) 99.170(4) 90 100.614(6) 92.630(10)
γ [ ο] 90 94.885(6) 90 90 90
Volume [Å3] 3723.0(3) 1866.9(2) 2851.8(3) 1500.57(17) 673.35(13)
Z 4 2 8 4 2
Calculated density [Mg/m3] 1.326 1.322 1.502 1.428 1.823
Absorption coefficient [mm–1] 0.714 0.712 2.076 1.973 1.997
F(000) 1544 772 1312 656 364
Crystal dimensions [mm] 0.26  0.17  0.06 0.32  0.16  0.09 0.23  0.14  0.03 0.41  0.32  0.11 0.47  0.10  0.07
θ range for data collection [°] 3.385 to 25.242 3.408 to 25.242 3.349 to 25.242 3.629 to 25.242 3.429 to 25.242
Index ranges -13r h r 13 -10r h r 13 -23 r h r22 -19r h r 18 -5 r h r5
-49 rk r 51 -12 rk r 14 -12r k r8 -10r k r 10 -19 rk r 17
-10r lr 15 -25 rl r27 -26 r lr 22  13r l r18 -16 rl r 11
Reflections collected 19426 17458 15267 7190 3841
Independent reflections 8770 8760 3590 3565 1631
Data/restraints/parameters 8770/ 0/ 452 8760/0/452 3590/0/156 3565/0/156 1631/0/80
Goodness-of-fit on F2 1.034 1.034 1.015 1.046 1.073
Final R indices [I 42s(I)] R1 ¼ 0.0536 R1 ¼ 0.0436 R1 ¼0.0504 R1 ¼ 0.0436 R1 ¼0.0399
wR2 ¼ 0.1366 wR2 ¼ 0.0961 wR2 ¼ 0.1168 wR2 ¼ 0.0851 wR2 ¼ 0.0704
R indices (all data)a R1 ¼ 0.0722 R1 ¼ 0.0680 R1 ¼0.0991 R1 ¼ 0.0779 R1 ¼0.0598
wR2 ¼ 0.1498 wR2 ¼ 0.1096 wR2 ¼ 0.1398 wR2 ¼ 0.1032 wR2 ¼ 0.0815
Largest diff. Peak and hole -0.596 and 0.981 -0.442 and 0.290 -0.375 and 0.448 -0.385 and 0.313 -0.853 and 0.563
CCDC number 1435983 1448536 1443743 1442340 1447888

1/2
⎛ 2⎞
a
⎝ ( )
R1 = ∑ F0 − Fc / ∑ Fc ; wR2 = ⎜ ∑ w(F02 − Fc2)2 / ∑ wF02 ⎟

GaussSum 3.0 [30] was used to calculate group contributions to these compounds are presented on the Fig. 1 and selected bond
the molecular orbitals and to prepare the partial density of states distances and angles are collected in Table S1 in Supplementary
(DOS) spectra. The electronic spectra were calculated with use of materials.
the CIS(D) (single excitation configuration interaction with dou- The (1) and (2) copper(I) coordination compounds belong to the
bles correction) method [31] and the PCM solvent model was used monoclinic P21/c and triclinic P–1space groups respectively. The Cu–
in the Gaussian calculations with acetonitrile as the solvent. N and Cu–O as well as Cu–P distances are normal and comparable to
literature values [20,22]. The distortion of the tetrahedral co-
ordination geometry for the compounds was estimated on the basis
3. Results and discussion of the structural τ4’ [32] parameter. Calculated values 0.87 for both
(1) and (2) compounds indicate some distortion from tetrahedron,
3.1. Syntheses and crystal structures although the deformation is relatively small considering that the
value 1 indicates an ideal tetrahedral geometry of the coordination
The coordination compounds were facilely synthesized by re- sphere. Zinc(II) compounds (3) and (4) crystalize in orthorhombic
fluxing the [Cu(PPh3)2NO3] and zinc(II) or cadmium(II) chloride Pbca and monoclinic P21/c space groups and the geometry of their
with appropriate picoline in methanol solvent and the crystals of coordination sphere has the same degree of deformation as in the
these compounds were obtained by slow evaporation of the re- case of copper(I) compounds (the same value of τ4’ parameter).
action mixtures. In solutions copper(I)-phosphine coordination Examination of packing diagrams of (3) and (4) reveals that both
compounds may be unstable and give rise to partial ligand dis- compounds exhibits intermolecular face-to-face stacking interac-
sociation and oxidation. Whereas both the copper(I) compounds in tion between parallel pyridine rings although the geometrical
display in 31P NMR spectra one, broad singlet (cf. Fig. S1). More- parameters indicate rather weak interaction due to distances of
over the UV–vis spectra of the acetonitrile solutions of these 3.68, 3.78 Å and shifts equal to 0.29 and 1.09 Å respectively (cf. Fig.
compounds do not show any changes during 26-h measurements. S2 in Supplementary materials). The structure of cadmium(II)
IR spectra display general characteristic features as expected from compound (5) is known [23] and it is an coordination polymer with
their structural formulas. The picoline νC ¼ N stretching bands 2-c uninodal net arranged in the [1 0 0] direction.
present maxima in the range from 1576 cm-1 to 1627 cm-1 wherein
in the lower range of frequency are bands of copper compounds 3.2. Photophysical properties
which indicates slightly weaker interaction between picoline li-
gand and the central ion. X-ray crystallography revealed that The UV–vis spectra of the coordination compounds were de-
compounds (1)–(4) adopt a mononuclear tetrahedral coordination termined in acetonitrile solutions and in solid state (reflectance
geometry. The ORTEP drawings of the molecular structures of spectra). Fig. 2 presents the absorption electronic spectra of zinc
130 J.G. Małecki, A. Maroń / Journal of Luminescence 186 (2017) 127–134

Fig. 1. ORTEP drawings of [Cu(PPh3)2(β-pic)NO3] (1), [Cu(PPh3)2(γ-pic)NO3] (2), [Zn(β-pic)Cl2] (3), [Zn(γ-pic)Cl2] (4) and asymmetric unit of [Cd(β-pic)Cl2]n (5). Hydrogen
atoms were omitted for clarity.

(II) coordination compounds (3) and (4). The remaining spectra are We perform the quantum theoretical calculations using density
shown on Fig. S3 in Supplementary materials. functional theory (DFT) in order to determine the composition of
Comparing the absorption spectra of the picolines and 3d metals the frontier molecular orbitals of the mononuclear coordination
coordination compounds can be observed a shift of the free ligands compounds (1)-(4). The density of states (DOS) in term of Mülliken
absorption maxim to the higher energy. Thus the blue shift upon population analysis were calculated using the GaussSum program
complexation indicates that in these molecules the intramolecular and Fig. 3 presents the composition of the fragment orbitals con-
charge transfer process takes place. Therefore the picoline molecule tributing to the molecular orbitals of the (1) and (3) coordination
enhances the acceptor properties which is especially evident in highly compounds with β-picoline ligand. The electronic structures of γ-
polar solvents such as acetonitrile. Indeed in solid states a red shift (or picoline (2) and (4) compounds are obviously similar.
lack of shift) of the absorption maximum corresponding to picoline In the frontier molecular orbitals of the coordination compounds
π-π* transition is observed (cf. Fig. 2 and Fig. S3). In the case of (1) and (2) the dCu orbitals play significant role with the share of
copper(I) compounds is also observed a significant reduction of the 50% in HOMO, 69% in HOMO-1 and 61% in the case of HOMO-2.
band intensity which can be related to the presence of other ligands as Whereas the LUMO and LUMOþ1 are mainly localized on the pi-
PPh3 and NO3– having the acceptor properties. coline moiety. In the case of zinc(II) compounds (3) and (4), and
J.G. Małecki, A. Maroń / Journal of Luminescence 186 (2017) 127–134 131

Fig. 2. UV–vis spectra of (3) and (4) coordination compounds in solid states (reflectance spectra) and acetonitrile solutions.

Fig. 3. Density of states (DOS) diagrams for compounds (1) and (3).

how it should be assumed for the compound (5), occupied higher transitions between inter– and intraligands.
orbitals are localized on the picoline and chloride ligands while The compounds both in solid states and in acetonitrile solu-
LUMOs are composed from methylpyridine orbitals (cf. Fig. 3). Thus tions reveal luminescence excited at a wavelength in the range
the UV–vis spectra (cf. Fig. S3) of the copper(I) compounds in the from 361 to 369 nm as can be seen from the data collected in
range of lower energies are dominated by combined metal-to-li- Table 2. The excitation wavelength corresponds to the H-2-L þ4
gand and ligand-to-ligand charge transfer transitions. The absorp- (81%) and HOMO-L þ6 (92%) transitions in the case of com-
tion bands of the zinc(II) and cadmium(II) compounds result from pounds (1) and (2) that is the nature of excitation can be described

Table 2
The emission data of the compound (1)-(5) and the picoline ligands.

compound medium λex (nm) λem (nm) (Φ (%)) Stokes shift τ, ns, (weight)
[cm-1]

(1) MeCN 276, 357,368, 424 496 (1.40) 7013 3.23 (29.99%), 6.87 (70.01%)
Solid 390, 341 529 (9.33) 6737 22560 (53.84%), 11590 (41.29%), 770 (4.87%)
77 K 310 483 11554 92740 (68.02%), 42050 (31.98%)
(2) MeCN 264, 355, 370, 420 491 (0.15) 6660 2.86 (10.88%), 7.66 (89.12%)
Solid — — — —
77 K 316 449 9373 64220 (68.55%), 150100 (31.45%)
(3) MeCN 274, 361 491 (10.04) 7334 1.50 (28.50%), 7.32 (71.50%)
Solid 421, 401, 322 478 (10.23) 2832 1.63 (61.52%), 4.09 (38.48)
77 K — — — —
(4) MeCN 271, 294, 355, 368, 423 500 (9.70) 7174 2.73 (15.66%), 7.19 (84.34%)
Solid –– 482 (16.40) 2970 1.02 (59.76%), 2.43 (40.24%)
77 K — — —
(5) MeCN 272, 291, 369, 427 490 (27.02) 6692 0.91 (2.54%), 6.45 (80.31%), 12.16 (17.16%)
Solid 331, 315 I: 341, 357, 371 886 9441 (91.75%), 2144 (8.25%)
77 K — II: 527 (39.53) — —

β-picoline MeCN 282, 308, 348, 387* 514 ( o0.01) 7.41
γ-picoline MeCN 274 401 (2.55%) 1.44 (61.11%), 3.35 (38.89%)

— non-emissive; bold marked are excitation wavelengths used to prepare emission spectra and to calculate the ΔEexc-em
132 J.G. Małecki, A. Maroń / Journal of Luminescence 186 (2017) 127–134

Fig. 4. Emission spectra of the (1)-(5) compounds and 3-methyl and 4-methylpyridines in acetonitrile solution (left) and luminescence of compound (1) in different
conditions (right). B – hypsochromic shift; R – bathochromic shift.

as (61%)dCu þ(28%)πNO3-π*PPh3 and (50%)dCu þ(44%)πPPh3- (88%) of the emissive excited states by metal supported (M þ X)LCT states
π*PPh3 þ(10%)π*picoline. For zinc(II) compounds were calculated the in which is involved NO3– ligand. The non-radiative decay con-
H-2-Lþ 1 (100%), H-3-LUMO (100%) and H-2-LUMO (100%) stants are considerably higher than radiative ones and in addition
transitions i.e. transitions between chloride and picoline ligands the solution of γ-picoline has greater quantum efficiency than the
(πCl-π*picoline). copper(I) complex (2). The confirmation of the quenching effect of
The emission spectra of the compounds in solid states and in NO3– ligand is to compare the obtained values with very high
acetonitrile solutions present Fig. 4 and Figs. S4, S5 in Supple- quantum yields (from 0.99 to 0.66) of [Cu(PPh3)2(γ-pic)X] com-
mentary materials. So, as can be seen the compounds display, in pounds, where X¼Cl, Br, I [22]. In solid state the luminescence is
different conditions, non-structured emission bands. Whereas the totally quenched in the case of γ-picoline compound (2) while β-
difference between β– and γ–picoline coordination compounds is picoline analogue (1) displays red shifted emission band with
the shift of emission maxima. The lack of structure in combination quantum yield about 9%. Moreover the emission lifetime is long,
with a significant bathochromic shift suggests a singlet state reaching a value of 19 ns. It is known that a large Stokes-like shift
emission of the γ-picoline coordination compounds. The com- occurs when compound undergoes a substantial structural re-
pounds with β-picoline in coordination sphere show a hypso- laxation in the excited state, It is evident that in solutions the
chromic shift of emission maxima compared to the free ligand (cf. compounds have a higher possibility to distortion than in solid,
Table 2 and Fig. 4). In the acetonitrile solutions, at ambient con- thus the values of Stokes shifts in solutions are greater. More im-
dition, the average decay times are in the nanosecond scale ran- portant is the difference between the values of the shift for the β-
ging from 6.3 to 8 ns (cf. Table 3). Due to the fact that polymeric and γ-picoline. The values for γ-picoline compounds are lower
structure of cadmium(II) compounds is not retained in solution than those for 3-methylpyridine. This fact indicates greater rigidity
the decay times and Stokes shifts in the case of the compounds of 4-methylpyridine compound associated with the stronger im-
(3) and (5) are similar. In addition some intermolecular interac- pact of methyl group in position 4 in pyridine ring. Moreover the
tions between [Cd(β-pic)Cl2] in the solution may be responsible Cu–Npy bond length is slightly shorter in the case of compound (2)
for the triple-exponential emission decay time in the solution (cf. (cf. Table S1), which additionally confirm a stronger interaction
Table 2). The emission lifetimes in solutions were estimated by the
between γ-picoline and copper(I) and consequently more rigid
least-square fitting of the emission decays using two exponentials
structure of this molecule in respect to the β-picoline one. Further
i.e. I ¼A1exp(  t/τ1)þA2exp(  t/τ2), where τ1 and τ2 are the life-
the methyl group in position 4 in γ-picoline enhances the 3LC state
times and A1 and A2 are the pre-exponential factors. The two
participation in excited states and reduces the value of quantum
decay components may be considered to be the emission from
yield (cf. Tables 2 and 3) relative to β-picoline compound (1).
different sites with the same electronic origin [22]. The radiative
Both zinc(II), (2) and (3), coordination compounds exhibit si-
constants kr of the compounds were estimated from the average
milar luminescence properties with very high Stokes shifts in so-
emission lifetime calculated with use of the following equations:
A1τ12 + A2 τ 22
lutions and relatively small in solid state which clearly indicates a
τav = A1τ1 + A2 τ 2
and k r = Φ/τav , k nr = k r (1 − Φ ) /Φ and the obtained significant share of the structural relaxation processes in solution.
data are collected in Table 3. For the compound (3) the time dependent density functional
The low quantum yield of the emission of copper(I) compounds theory calculations were carried out using the optimized geo-
(1) and (2) indicates the participation of the thermal deactivation metry. The calculations show that the HOMO-1-LUMO transition

Table 3
Luminescence properties of the compounds (1)-(5) in acetonitrile solution and solid state.

Compound acetonitrile solutions solid state

a
(1) (2) (3) (4) (5) (1) (2) (3) (4) (5)

Φ {%] 1.40 0.15 10.04 16.40 27.02 9.33 – 9.70 10.23 39.53
τav [ns] 6.26 7.45 6.88 6.90 7.69 18.99 – 4.38 7.52 10604.06
kr [s-1] 2.23.106 2.01.106 1.46.107 2.38.107 3.51.109 4.90.106 – 2.21.107 1.36.107 3.73.104
knr [s-1] 1.57.108 1.34.109 1.31.108 1.21.108 9.48.109 4.76.107 – 2.06.108 1.19.108 5.70.104

a
the τav was calculated using three exponentials equation.
J.G. Małecki, A. Maroń / Journal of Luminescence 186 (2017) 127–134 133

contribute to the lowest singlet excited state by 100% and the state designated for the [Cu(PPh3)2(picoline)(NO3)] compounds with
is assignable to the chloride-to-picoline charge transfer (XLCT) extremely efficient halide analogues is evident that NO3– ligand
state. The molecule of compound (3) in excited state is flattened effectively quenches the emission. Whereas the coordination of
with respect to the ground state, which reflects the lower value of the picolines to zinc(II) chloride increases the emission efficiency
the τ4’ parameter equal to 0.57 (geometrical parameter for S1 state shifting the maxima to the green range of the visible spectrum.
are given in Table S3). It seems obvious that, correspondingly, is for The most efficient emission has been designated for cadmium(II)
the second zinc(II) compound (4) and the cadmium(II) compound coordination compound, which has polymeric structure. In solid
(5). The small value of Stokes shift measured for compound (5) in state at room temperature the quantum efficiency of the com-
solid state indicates a high rigidity of the polymer chains. pound is about 40% and the average lifetime of the excited state
At low, liquid nitrogen, temperature emissive are only copper reaches to 10.6 μs. The emission of zinc(II) and cadmium(II) co-
(I) compounds wherein the excitation and emission maxima are ordination compounds originated from chloride-to-picoline
blue shifted compared to solutions at ambient temperature. Since charge transfer (XLCT) states.
the analogous halogen compounds i.e. [Cu(PPh3)2(β-pic)X], where
X ¼halogen [22], exhibit typical red-shift of emissions maxima at
77 K, additionally the shifts towards a higher energies in the cases Acknowledgements
of studied compounds (1) and (2) must be associated with the
presence of NO3– ligand in the coordination sphere. The decay Calculations have been carried out in Wroclaw Centre for
times at 77 K are very long equal to 84.3 μs for (1) and 108.7 μs for Networking and Supercomputing (http://www.wcss.wroc.pl) grant
(2) which indicate the phosphorescence. The lack of emission at no. 18.
liquid nitrogen temperature of the zinc(II) and cadmium(II) com-
pounds (3)–(5) may be connected on the one hand with the triplet
states of emission 3(M þXLCT) types which are deactivated on the Appendix A. Supporting information
non-radiative path. On the other hand should take into account
the presence of the stacking interaction between picoline rings Supplementary data associated with this article can be found in
which may cause emission quench increasing the possibility of the the online version at http://dx.doi.org/10.1016/j.jlumin.2017.02.025.
energy dissipation.
The role of the nitrate ligand in copper(I) compounds can be
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