Three nickel(II) and zinc(II) complexes with two novel nitronyl nitroxide ligands: Syntheses, crystal structures, and luminescent properties

Article abstract of DOI:10.1002/zaac.201200151

To explore the coordination abilities of nitronyl nitroxide ligands, two ligands substituted with quinoxaline (L¹) and 2-phenyl-1, 2, 3-triazole (L²) and their Ni^II and Zn^II complexes: Ni(L¹)(hfac)₂ (1), Ni(L²)(hfac) ₂ (2), and Zn(L²)(hfac)₂ (3) (hfac = hexafluoroacetylacetonate), were synthesized and characterized. X-ray single-crystal diffraction analysis shows that compound 1 has a mononuclear structure, which is further linked into a three-dimensional (3D) supramolecular network by C-H...F hydrogen-bonding, C-H...π, and π...π stacking interactions. Complexes 2 and 3 have similar mononuclear structures, which are further linked into one-dimensional (1D) supramolecular chains by various intermolecular weak interactions, such as C-H...F hydrogen-bonding, and π...π stacking interactions. The results indicate that the steric bulk of L¹ and L² and the existence of hexafluoroacetylacetonate (hfac) play important roles in controlling the formation of the final frameworks of complexes 1-3. Moreover, the luminescent properties of the ligands and their complexes were investigated in detail. Copyright

Full text of DOI:10.1002/zaac.201200151

Job/Unit: Z12151
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Date: 30-07-12 14:48:43
Pages: 7
ARTICLE
DOI: 10.1002/zaac.201200151
Three Nickel(II) and Zinc(II) Complexes with Two Novel Nitronyl Nitroxide
Ligands: Syntheses, Crystal Structures, and Luminescent Properties
You-Juan Zhang,[a] Jun-Jie Wang*[a] and Jing Chen*[a]
Keywords: Zinc; Nickel; Nitronyl nitroxide; Crystal structures; Luminescent properties
Abstract. To explore the coordination abilities of nitronyl nitroxide
ligands, two ligands substituted with quinoxaline (L1) and 2-phenyl-
tures, which are further linked into one-dimensional (1D) supramolec-
ular chains by various intermolecular weak interactions, such as C–
1,2,3-triazole (L2) and their NiII and ZnII complexes: Ni(L1)(hfac)2 H···F hydrogen-bonding, and π···π stacking interactions. The results
(1), Ni(L2)(hfac)2 (2), and Zn(L2)(hfac)2 (3) (hfac = hexafluoroacet-
indicate that the steric bulk of L1 and L2 and the existence of hexafluo-
ylacetonate), were synthesized and characterized. X-ray single-crystal roacetylacetonate (hfac) play important roles in controlling the forma-
diffraction analysis shows that compound 1 has a mononuclear struc-
ture, which is further linked into a three-dimensional (3D) supramolec-
ular network by C–H···F hydrogen-bonding, C–H···π, and π···π stack-
ing interactions. Complexes 2 and 3 have similar mononuclear struc-
tion of the final frameworks of complexes 1–3. Moreover, the lumines-
cent properties of the ligands and their complexes were investigated
in detail.
not only play important roles in the formation of the com-
plexes, but can also exert a deciding influence on their struc-
tures and functions (or properties).
Introduction
Currently, there is considerable interest in the design and
synthesis of metal complexes not only due to their intriguing
structural diversity but also because of their potential applica-
tions in molecular adsorption and separation processes, gas
storage, ion exchange, catalysis, sensor technology and so
on.[1,2] The choice of suitable organic ligands favoring struc-
ture-specific self-assembly is crucial for the construction of
prospective coordination structures with relevant properties
and functions.[3] Nitronyl nitroxide radicals as stable organic
functional groups have played prominent roles in the design
and construction of molecular materials, which is especially
interesting for magnetic interactions between the central metal
atoms in coordination polymers.[4] For functional groups, it is
desirable to use combinations of donor groups, which lead to
stereochemical non-rigid compounds with potentially higher
coordination numbers of the metal ion. Thus, nitronyl ni-
troxides with polynitrogen heterocyclic substituents such as
imidazole,[5] benzimidazole,[6] pyrazole,[7] 1,2,4-triazole,[8]
and tetrazole[9] have been prepared. Ligand substituents, as an
important part of the ligand, as well as auxiliary ligands,
counteranions, the pH values of the reaction solutions, tem-
perature, molar ratio between reactants, and solvent system[10]
Considering all aspects stated above, our idea in this work
was to select two nitronyl nitroxide ligands with quinoxaline
(L1) and 2-phenyl-1,2,3-triazole (L2) (Scheme 1), to construct
a series of NiII and ZnII coordination compounds: Ni(L1)(hfac)2
(1), Ni(L2)(hfac)2 (2), and Zn(L2)(hfac)2 (3) (hfac = hexafluo-
roacetylacetonate). Furthermore, the luminescent properties of
the ligands and their complexes in the solid state at room tem-
perature were investigated.
Scheme 1.
Experimental Section
Materials and Methods: 2-Phenyl-1,2,3-triazole-4-carboxaldehyde[11]
and quinoxaline-2-carboxaldehyde[12] were prepared and purified ac-
cording to the methods reported. M(hfac)2·2H2O (M = Ni or Zn, hfac
= hexafluoroacetylacetone) were prepared as previous reported.[13] Ni-
tronyl nitroxide radical was synthesized according to reported literature
procedure.[14] Other reagents and solvents for synthesis were commer-
cially available and used as received or purified by standard methods
prior to use. Elemental analyses (C, H, N) were performed with a
Perkin-Elmer 240C analyzer. The IR spectra were measured with a
Varian 800 (Scimitar Series) FT-IR spectrometer as KBr pellets. The
* Dr. J.-J. Wang
Fax: +86-372-2900040
E-Mail: adamwjj@yahoo.com.cn
Prof. Dr. J. Chen
Fax:+86-372-2900040
E-Mail: chenjinghao2008@163.com
[a] College of Chemistry and Chemical Engineering
Anyang Normal University
Anyang, Henan 455002, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201200151 or from the au-
thor.
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Y.-J. Zhang, J.-J. Wang, J. Chen
ARTICLE
emission spectra in solid state at room temperature were taken with a 1206 s, 1137 s, 1101 m, 1021 w, 986 w, 950 w, 901 w, 865 w, 806 m,
Cary Eclips fluorescence spectrophotometer.
791 m, 759 m, 740 w, 674 s, 629 w, 587 m, 545 w, 525 w, 454 w, 417
w cm–1.
Preparation of Ligands L1 and L2: L1 was obtained by condensation
of quinoxaline-2-carboxaldehye with 2,3-bis(hydroxylamino)-2,3-di-
methylbutane, followed by chemical oxidation with sodium periodate for 1 was used for this compound except that L1 was replaced by L2.
in the chloroform and water solution at 0 °C. After separation, the Dark blue single crystals suitable for X-ray analysis were obtained
chloroform solution was concentrated to 10 mL. Afterwards, n-hexane after cooling to room temperature. Yield: ca. 30% based on L2.
Preparation of Ni(L2)(hfac)2 (2): A similar procedure as described
(50 mL) was added. The solution was kept at 4 °C for one week to give
green solid products. Yield: ca. 60%. C15H17N4O2 (285.33): calcd. C
63.13; H 6.01; N 19.64%; found: C 63.31; H 6.12; N 19.44%. IR
C25H22F12N5O6Ni (775.19): calcd. C 38.76, H 2.86, N 9.05%; found:
C, 38.24, H, 2.99, N, 9.44%. IR (KBr): ν˜ = 3061 m, 2997 m, 2947
m, 1648 s, 1587 w, 1540 m, 1515 m, 1492 s, 1455 m, 1400 m, 1375
(KBr): ν˜ = 3382 w, 3064 w, 2994 m, 2943 w, 2875 w, 2577 w, 1680 s, 1362 m, 1347 w, 1331 m, 1262 s, 1207 s, 1137 s, 1099 m, 1022 w,
w, 1642 w, 1610 w, 1568 w, 1541 w, 1506 m, 1488 m, 1468 m, 1453
m, 1417 s, 1370 s, 1325 m, 1281 w, 1250 w, 1213 m, 1175 m, 1132
m, 1012 w, 984 m, 962 m, 928 w, 898 w, 861 w, 798 w, 769 m, 682
w, 645 w, 613 w, 572 w, 540 m, 483 w, 450 m, 419 m cm–1.
986 w, 950 w, 902 w, 864 w, 806 m, 791 m, 759 m, 741 w, 674 s, 625
w, 587 m, 545 w, 525 w, 454 w, 419 w cm–1.
Preparation of Zn(L2)(hfac)2 (3): A similar procedure as described
for 2 was used for this compound except that Ni(hfac)2·2H2O was
L2 was obtained through the same method except that quinoxaline-2- replaced by Zn(hfac)2·2H2O. Blue single crystals suitable for X-ray
carboxaldehye was replaced by 2-phenyl-1,2,3-triazole-4-carboxal-
dehye. Dark blue solid products appeared at the tube wall after ca. two
analysis were obtained after cooling to room temperature. Yield: ca.
40% based on L2. C25H22F12N5O6Zn (781.85): calcd. C 38.46, H 2.84,
weeks at room temperature. Yield: ca. 70%. C15H18N5O2 (300.34): N 8.98%; found: C 38.83, H 2.99, N 8.73%. IR (KBr): ν˜ = 3003 m,
calcd. C 59.97; H 6.04; N 23.33%; found: C 60.22; H 6.33; N 23.03%.
IR (KBr): ν˜ = 3159 w, 3063 w, 2990 m, 2940 w, 1597 m, 1499 m,
1472 m, 1454 m, 1440 m, 1414 s, 1368 s, 1350 s, 1213 m, 1172 m,
1138 m, 1071 w, 1028 m, 965 m, 859 w, 817 w, 759 m, 696 m, 667
m, 603 w, 541 w, 493 w, 465 w cm–1.
1648 s, 1597 w, 1555 m, 1528 m, 1498 s, 1384 w, 1369 s, 1326 w,
1257 s, 1207 s, 1146 s, 1097 m, 1036 w, 976 w, 917 w, 875 w, 807
w, 795 m, 767 m, 742 w, 693 w, 669 s, 615 w, 585 m, 540 w, 525 w,
479 w, 454 w, 404 w cm–1.
X-ray Crystallographic Studies of 1–3: Single-crystal X-ray studies
for compounds 1–3 were performed with a Bruker APEX-II CCD dif-
fractometer at 293(2) K and R-AXIS-IV diffractometer at 291(2) K,
Preparation of Ni(L1)(hfac)2 (1): A solution of Ni(hfac)2·2H2O
(0.1 mmol) was dissolved in boiling n-heptane (25 mL). The solution
was further heated for 30 min and afterwards cooled down to 60 °C, respectively. The determinations of unit cell parameters and data col-
whereupon L1 (0.1 mmol) was added whilst stirring followed by the lections were performed with Mo-Kα radiation with radiation wave-
addition of CH2Cl2 (5 mL). The solution was kept at 4 °C for two
length of 0.71073 Å by using the ω-scan technique. Lorentz polariza-
weeks. Black green single crystals suitable for X-ray analysis were tion and absorption corrections were applied by using the multiscan
obtained. Yield: ca. 50% based on L1. C25H21F12N4O6Ni (760.17):
calcd. C 39.52, H 2.79, N 7.38%; found: C 39.13, H 2.59, N 7.73%.
IR (KBr): ν˜ = 3061 m, 2988 m, 2947 m, 1648 s, 1587 w, 1554 m, SHELXL-97 programs.[16] Metal atoms in each compound were lo-
program.[15] The structures were solved by direct methods and refined
with the full-matrix least-squares technique using the SHELXS-97 and
1486 s, 1456 m, 1400 m, 1375 s, 1362 m, 1347 w, 1331 m, 1262 s,
cated from the E-maps, and other non-hydrogen atoms were located
Table 1. Crystallographic data and structure refinement summary for compounds 1–3.
1
2
3
Chemical formula
Formula weight
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
C25H21F12N4O6Ni
760.17
C25H22F12N5O6Ni
775.19
C25H22F12N5O6Zn
781.85
triclinic
triclinic
triclinic
¯
¯
¯
P1
P1
P1
10.247(2)
11.153(2)
14.460(3)
73.27(3)
73.74(3)
80.57(3)
1513.1(5)
2
10.008(2)
11.971(2)
14.658(3)
78.34(3)
76.93(3)
68.75(3)
1580.3(5)
2
10.339(2)
11.606(2)
14.720(3)
79.48(3)
76.62(3)
67.32(3)
1577.0(5)
2
γ /°
V /Å3
Z
D /g·cm–3
F(000)
1.668
766
0.762
1.629
782
0.732
1.647
786
0.897
μ /mm–1
Collected reflections
Unique reflections
Rint
13540
7476
0.0195
1.049
4733
4733
0.0000
1.061
56709
7783
0.0312
1.082
GOF
T /K
293(2)
291(2)
0.0785
0.2410
0.441 / –0.622
293(2)
R1 [I Ͼ 2σ(I)]a)
wR2 (all data)b)
ρmax/ρmin /e·Å–3
0.0606
0.1898
1.102 / –0.614
0.0712
0.2418
0.965 / –0.606
a) R = Σ(||Fo|–|Fc||)/Σ|Fo|. b) wR = [Σw(|Fo|2–|Fc|2)2/Σw(Fo )]1/2
.
2
2
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Nickel(II) and Zinc(II) Complexes with Nitronyl Nitroxide Ligands
ges.[19] It is worth noting that the substituents of L1 and L2
and hfac play important roles in the formation of these supra-
molecular frameworks.
in successive difference Fourier syntheses and refined with anisotropic
thermal parameters on F2. Hydrogen atoms on carbon atoms of ligands
were placed in calculated, ideal positions and refined as riding on their
respective carbon atoms. For 2, a part of the fluorine atoms were re-
fined in disordered modes. Further detailed crystallographic data are
summarized in Table 1. Selected bond lengths and angles are listed
in Tables S1–S3 in the Supporting Information.
Crystallographic data (excluding structure factors) for the structures
in this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-862579, CCDC-779191, and CCDC-862580 (1–3)
(Fax:
+44-1223-336-033;
E-Mail:
deposit@ccdc.cam.ac.uk,
http://www.ccdc.cam.ac.uk).
Supporting Information (see footnote on the first page of this article):
Selected bond lengths and angles and excitation and emission spectra
of the ligands L1 and L2 as well as complexes 1–3.
Results and Discussion
Synthesis and General Characterizations
The syntheses of complexes 1–3 were carried out by the
reactions of Ni(hfac)2·2H2O or Zn(hfac)2·2H2O with L1 or L2.
Using the counteranion hfac is an important factor in the for-
mation of these compounds.
Complexes 1–3 are all air stable. All general characteriza-
tions were carried out on the crystal samples. The elemental
analyses of 1–3 were in good agreement with the results of the
structural analysis. In general, the IR spectra show features
attributable to each component of the compounds.[17] The ν(N–
O) band for 1–3 at 1375–1369 cm–1, which is similar to the
value 1370–1368 cm–1 of the ν(N–O) band of free L1 or L2,
indicates that one oxygen atom of L1 or L2 is not coordinated
to the NiII or ZnII ion. For complexes 1–3, the characteristic
ν(N–O) bands appeared in the usual region at 1146–1137 cm–1
(1137 cm–1 for 1, 1137 cm–1 for 2, and 1146 cm–1 for 3) and
are attributable to the corresponding coordination mode of
ν(N–O), which is in good agreement with the results of crystal
structure analysis.[18]
Descriptions of Crystal Structures for Compounds Ni(L1)
(hfac)2 (1), Ni(L2)(hfac)2 (2), and Zn(L2)(hfac)2 (3)
Complexes 1–3 are herein described in detail [Figure 1 and
Table S1 (Supporting Information) for 1, Figure 2 and Table
S2 for 2 as well as Figure 3 and Table S3 for 3]. X-ray single-
crystal diffraction analysis reveals that each asymmetric unit
of 1–3 contains one central MII atom, one L ligand, and two
hfac ions. In other words, each central MII atom is coordinated
by one oxygen atom and one nitrogen atom from one L1 (or
L2) ligand and four oxygen atoms from two hfac ions to com-
plete a distorted octahedral coordination environment [M–O =
2.002(4)–2.074(3), M–N = 2.152(2)–2.401(3) Å]. The hfac
ions act as typical chelating ligands to form a mononuclear
Figure 1. (a) ORTEP view of 1 with 30% thermal ellipsoid probability.
(b) The 2D supramolecular layer showing the intermolecular C–H···F
and π···π stacking interactions. (c) The 2D supramolecular layer show-
ing the intermolecular C–H···F, C–H···O and π···π stacking interactions
(partial hydrogen atoms are omitted for clarity).
For 1, the neutral mononuclear Ni(L1)(hfac)2 molecules are
structure. All M–N and M–O bond lengths as well as the bond assembled into 2D sheets and further to a 3D supramolecular
angles around each central MII atom are in the expected ran- network by intermolecular C–H···F hydrogen bonding
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Figure 2. (a) ORTEP view of 2 with 30% thermal ellipsoid prob-
ability: (b) The 1D supramolecular chain showing the intermolecular
C–H···F and π···π stacking interactions (partial hydrogen atoms are
omitted for clarity).
Figure 3. (a) ORTEP view of 3 with 30% thermal ellipsoid probability.
(b) The 1D supramolecular chain showing the intermolecular C–H···F
and π···π stacking interactions (partial hydrogen atoms are omitted for
clarity).
[C(8)···F(12A) separation: 3.348(5) Å; C(8)–H(8)···F(12A) an-
gle: 159.72°; symmetry code: A = –x+1, –y+1, –z+2],[20]
C–H···O hydrogen bonding [C(17)···O(2B) separation:
3.438(3) Å; C(17)–H(17)···O(2B) angle: 163.16°; symmetry
code: B = –x+2, –y+1, –z+2],[21] C–H···π interactions via edge-
to-face orientation between hfac and the pyrazine rings of L1
[d = 3.162(1) Å and A = 136.19° in the C–H···π patterns],[22]
π···π stacking interactions between parallel benzene rings from
adjacent L1 ligands with a centroid-centroid separation of
3.978(8) Å, and an interplanar separation of 3.682(6) Å (Fig-
ure 1b,c).[23] Whereas for 2 and 3, the neutral mononuclear
molecules are arranged into a 1D chain by C–H···F hydrogen
bonding [C(8)···F(12C) separation: 3.271(0) Å; C(8)–H(8)
···F(12C) angle: 152.27°; symmetry code: C = –x+2, –y+2, –
z+1 for 2; C(18)···F(6D) separation: 3.328(5) Å; C(18)–H(18)
azole rings from adjacent L2 ligands with centroid-centroid
separations of 3.653(2) Å for 2 and 3.723(6) Å for 3 and in-
terplanar separations of 3.564(1) Å for 2 and 3.657(8) Å for 3
(Figure 2b and Figure 3b).[23]
These observations indicate that the steric bulk of L1 and
L2 plays an important role in the formation of complexes 1–
3. Moreover, the existence of hfac plays an important role in
controlling the formation of the final frameworks of 1–3.
Luminescent Properties
Luminescent compounds are currently of great interest be-
···F(6D) angle: 130.03°; symmetry code: D = –x, –y+2, –z+1 cause of their various applications in chemical sensors, photo-
for 3],[20] and π···π stacking interactions between parallel tri- chemistry, and electroluminescent (EL) displays.[24] To exam-
4
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Nickel(II) and Zinc(II) Complexes with Nitronyl Nitroxide Ligands
ine the luminescent properties of compounds with nitronyl ni- and L2 and the existence of hexafluoroacetylacetonate (hfac)
troxide ligands, the luminescent properties of complexes 1–3 play important roles in controlling the formation of the final
and corresponding ligands in the solid state were investigated frameworks of 1–3. Moreover, complexes 1–3 can be excited
at room temperature. In this work, meanwhile, the individual directly and emit strong fluorescence at room temperature,
excitation/emission spectra for each compound 1–3 as well as which may make them excellent candidates for green fluores-
free ligands L1 and L2 are separately shown in Figures S2 and cent materials.
S1 (Supporting Information) for clarity. As shown in Figure 4,
it is obvious that there is one emission peak at 530 nm for 1
Acknowledgement
(λex = 389 nm), which is accompanied by the fact that the free
ligand L1 has one emission peak at 533 nm upon excitation at
λ = 391 nm. The free ligand L2 displays green luminescence
in the solid state at λmax = 532 nm upon excitation at λ =
390 nm; under the same experimental conditions, compounds
2 and 3 exhibit an intense luminescent emission at λmax = 532
and 530 nm upon excitation at 390 nm in the green fluorescent
region, respectively (Figure 4). The emission peaks of 1–3 are
similar to those of the corresponding ligands L1 and L2, which
are neither metal-to-ligand charge transfer (MLCT) nor ligand-
to-metal charge transfer (LMCT) in nature because NiII or ZnII
ions are difficult to oxidize or reduce to their d10 configura-
tion.[25,26] This phenomenon can be tentatively assigned to in-
traligand transfer π*–π transitions, namely, ligand-to-ligand
charge transfer (LLCT), similar to the results reported on coor-
dination polymers with an aromatic backbone.[25] The different
relative intensities of 1–3 may be assigned to structural diversi-
ties and different ratios of the L1 and L2 ligands, or to the
strong conjugation and inter/intramolecular interaction be-
tween the molecule segments of ligands.[25–27]
This work was financially supported by the National Natural Science
Foundation of China (No. 21071006), the Natural Science Foundation
of Henan Province (Nos. 102102210457 and 112102210371), the Nat-
ural Science Foundation of the Henan Higher Education Institutions
of China (Nos. 2010B150001 and 12B150003) and the Industrial Re-
search Project of Technology Bureau of Anyang (No. 39).
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Figure 4. Solid emission spectra of L1 and L2 and 1–3 at room tem-
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Conclusions
We synthesized two novel nitronyl nitroxide ligands and
their three mononuclear NiII and ZnII complexes, which were
further linked into higher-dimensional supramolecular net-
works by various intermolecular weak interactions, such as C–
H···F or C–H···O hydrogen-bonding, C–H···π, and π···π stack-
ing interactions. The results indicate that the steric bulk of L1
Z. Anorg. Allg. Chem. 0000, 0–0
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Job/Unit: Z12151
/KAP1
Date: 30-07-12 14:48:43
Pages: 7
Y.-J. Zhang, J.-J. Wang, J. Chen
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Received: March 30, 2012
Published Online: ᭿
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z12151
/KAP1
Date: 30-07-12 14:48:43
Pages: 7
Nickel(II) and Zinc(II) Complexes with Nitronyl Nitroxide Ligands
Y.-J. Zhang, J.-J. Wang,* J. Chen .................................... 1–7
Three Nickel(II) and Zinc(II) Complexes with Two Novel Ni-
tronyl Nitroxide Ligands: Syntheses, Crystal Structures, and
Luminescent Properties
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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