Syntheses, characterization, and luminescent properties of monoethylzinc complexes with anilido-imine ligands

Article abstract of DOI:10.1002/ejic.200700182

The syntheses of three anilido-imine ligands of the general formula ortho-C₆H₄(NHAr′)(CH=NAr″ [Ar′ = 7-(2,4-Me₂)C₉H₄N, Ar″ = 2,6-Me ₂C₆H₃ (2a); Ar′ = 7-(2,4-Me _2<

Full text of DOI:10.1002/ejic.200700182

FULL PAPER
DOI: 10.1002/ejic.200700182
Syntheses, Characterization, and Luminescent Properties of Monoethylzinc
Complexes with Anilido–Imine Ligands
Qing Su,[a] Wei Gao,[a] Qiao-Lin Wu,[a] Ling Ye,[a] Guang-Hua Li,[b] and Ying Mu*[a]
Keywords: Luminescence / N ligands / Quinoline / Zinc
The syntheses of three anilido–imine ligands of the general
formula ortho-C6H4(NHArЈ)(CH=NArЈЈ [ArЈ = 7-(2,4-Me2)-
C9H4N, ArЈЈ = 2,6-Me2C6H3 (2a); ArЈ = 7-(2,4-Me2)C9H4N,
ArЈЈ= 2,6-Et2C6H3 (2b); ArЈ = 7-(2,4-Me2)C9H4N, ArЈЈ= 2,6-
iPr2C6H3 (2c)] and four zinc(II) complexes of the general for-
elimination. All compounds were characterized by elemental
analysis and 1H and 13C NMR spectroscopy. The molecular
structures of compounds 2a, 2b, 3b, and 3c were determined
by single-crystal X-ray crystallography. The X-ray analysis
reveals that complexes 3b and 3c exist in the dimeric form
with the N atom in the quinolyl ring coordinating to the other
Zn atom to make the Zn atoms four coordinate. Luminescent
properties of ligands 2a–2d and complexes 3a–3d in both
solution and the solid state were studied.
mula [ortho-C6H4(NHArЈ)(CH=NArЈЈ)]ZnEt [ArЈ
= 7-(2,4-
Me2)C9H4N, ArЈЈ= 2,6-Me2C6H3 (3a); ArЈ = 7-(2,4-Me2)-
C9H4N, ArЈЈ= 2,6-Et2C6H3 (3b); ArЈ = 7-(2,4-Me2)C9H4N, ArЈЈ
= 2,6-iPr2C6H3 (3c); ArЈЈ = 2,6-Me2C6H3, ArЈЈ = 2,6-iPr2C6H3
(3d)] are described. The complexes were synthesized from
the reaction of ZnEt2 with corresponding ligands 2 by alkane
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
materials considering that the anilido–imine ligands and the
salicylaldiminate ligands have similar structures. Recently,
Lee et al. reported some dinuclear ZnII complexes with anil-
ido–imine ligands.[11] As we are interested in tuning the lu-
minescent properties of ZnII complexes by modification of
the ligands and the coordination geometries of ZnII com-
plexes, we synthesized three new anilido–imine ligands with
a 7-amino-2,4-dimethylquinolyl chromophore, in which the
nitrogen atom in the quinolyl ring might coordinate to the
ZnII in another molecule to form dinuclear or polynuclear
ZnII complexes. The results indicate that all three ZnII com-
plexes with quinolyl exist in a novel dimeric form. Herein
we report the syntheses, characterizations, and fluorescent
properties of four new zinc complexes with anilido–imine
ligands, ortho-C6H4(NHArЈ)(CH=NArЈЈ)ZnEt [ArЈ = 7-
(2,4-Me2)C9H4N, ArЈЈ = 2,6-Me2C6H3 (3a); ArЈ = 7-(2,4-
Me2)C9H4N, ArЈЈ = 2,6-Et2C6H3 (3b); ArЈ = 7-(2,4-Me2)-
C9H4N, ArЈЈ = 2,6-iPr2C6H3 (3c); ArЈ = 2,6-Me2C6H3, ArЈЈ
= 2,6-iPr2C6H3 (3d)].
Introduction
Zinc(II) complexes as luminescent materials have been
extensively studied in recent years.[1–9] Among these known
luminescent Zn complexes, the ligands are mainly benzothi-
azolates,[1] quinolinolates,[2] salicylideneaminates,[3] dipyr-
rin,[6c] N-7-azaindolyl,[8] and 2,2Ј-dipyridylamino.[9] As ZnII
with a closed shell is spectroscopically silent in essence, the
luminescent properties of ZnII complexes can be easily
tuned by the modification of the ligands. Meanwhile, ZnII
complexes can have relatively flexible coordination numbers
ranging from three-coordinate to six-coordinate depending
on the structure of their ligands. Bis(8-hydroxyquinoline)-
zinc(II) (Znq2) was reported to be a good electrolumin-
escent (EL) material that exists in the form of (Znq2)4.[2]
Bis[2-(2-hydroxyphenyl)benzothiazolate]zinc [Zn(BTZ)2]2
was found to be an excellent white EL material.[1] Some
polynuclear ZnII complexes[7,8] were also reported to have
intriguing structural and photoluminescent properties. We
reported a number of aluminum[10a,10b] and boron[10c] com-
plexes with chelating anilido–imine ligands showing good
luminescent properties. Similarly, zinc complexes with the
anilido–imine ligands might also be efficient luminescent
Results and Discussion
Syntheses of the Ligands
[a] Key Laboratory for Supramolecular Structure and Materials of
Ministry of Education, School of Chemistry, Jilin University,
2699 Qianjin Street, Changchun 130012, People’s Republic of
China
Preligands 1a–1c ortho-C6H4F(CH=NArЈЈ) [ArЈЈ = 2,6-
Me2C6H3 (1a), 2,6-Et2C6H3 (1b), 2,6-iPr2C6H3 (1c)] were
synthesized by a condensation reaction of ortho-fluorobenz-
aldehyde with 1 equiv. of the relevant amine in n-hexane in
the presence of anhydrous MgSO4 according to a modified
literature method.[12] Among them, 1b is a new compound
and characterized by NMR spectroscopy along with ele-
[b] State Key Laboratory of Inorganic Synthesis and Preparative
Chemistry, School of Chemistry, Jilin University,
2699 Qianjin Street, Changchun 130012, People’s Republic of
China
Fax: +86-431-85193421
E-mail: ymu@mail.jlu.edu.cn
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Monoethylzinc Complexes with Anilido–Imine Ligands
mental analysis. The imino CH proton of compound 1b ex- Syntheses of the Complexes
hibits resonance at δ = 8.55 ppm and the corresponding
Treatment of 2a–2d with 1 equiv. of ZnEt2 in toluene
imino CH carbon exhibits resonance at δ = 156.1 ppm. At
room temperature, 1b exists in the form of a yellow oil but
as a yellow solid at lower temperatures. It can be purified
by reduced-pressure distillation. Three new ligands, ortho-
C6H4(NHArЈ)(CH=NArЈЈ) [ArЈ = 7-(2,4-Me2)C9H4N, ArЈЈ
= 2,6-Me2C6H3 (2a); ArЈ = 7-(2,4-Me2)C9H4N, ArЈЈ = 2,6-
Et2C6H3 (2b); ArЈ = 7-(2,4-Me2)C9H4N, ArЈЈ = 2,6-
iPr2C6H3 (2c)], were synthesized by nucleophilic aromatic
substitution of fluoride in 1a–1c by 7-amino-2,4-dimethyl-
quinoline lithium salt according to a modified literature
caused the elimination of ethane and afforded the corre-
sponding monoethylzinc complexes 3a–3d in good yields
(78–85%). All complexes have good solubility in common
solvents, such as toluene, dichloromethane, diethyl ether,
THF, and n-hexane. All complexes were characterized by
1H and 13C NMR spectroscopy as well as elemental analy-
sis, and satisfactory analytic results were obtained. The N–
H proton signals of the free ligands disappear, and the new
Zn–CH2 proton signals appear at a higher field (0.55–
0.02 ppm) in the 1H NMR spectra of complexes 3a–3d,
which is indicative of the formation of Zn–N bond in these
compounds. The Zn–CH2 carbon signals in the 13C NMR
spectra are observed at –1.2 (for 3a), –1.8 (for 3b), –1.3 (for
3c), and –2.9 (for 3d) ppm. The two methyl groups of the
isopropyl units in complex 3c are inequivalent, for the coor-
dination of the anilido–imine ligands to the zinc center
causes the rotation about the N–aryl bond to become slow
on the NMR timescale.[10a] All complexes have pretty good
thermal stability and can be heated in boiling toluene for
several hours without obvious decomposition. All com-
plexes are air- and/or moisture-sensitive in solution and the
solid state.
1
procedure[12] (Scheme 1) and characterized by H and 13C
NMR spectroscopy along with elemental analysis. Ligands
2a and 2b were purified by chromatography on silica gel
with ethyl acetate/petroleum ether as the eluent to give pure
products as yellow crystals, whereas compound 2c was puri-
fied by crystallization from methanol. For comparison, li-
gand 2d[13] was synthesized according to a literature method
and characterized by 1H NMR spectroscopy. The 1H NMR
spectra of 2a–2c exhibit resonances in the range of δ = 8.35–
8.37 ppm for the imino CH proton, whereas the corre-
sponding 13C NMR resonances are in the range of δ =
165.6–165.8 ppm. The NH proton resonance in 2a–2c ap-
pears at relatively low field (δ = 11.64, 11.62, and
11.59 ppm, respectively) relative to those in compound
2d[13] (δ =10.50 ppm) and other reported compounds of this
type [δ =10.53 ppm for ortho-C6H4{NH(C6H3iPr2-2,6)}-
[CH=NC6H3Me2-2,6],[10b] 10.60 ppm for ortho-C6H4-
Crystal Structures
The molecular structures of ligands 2a and 2b as well as
{NH(C6H3Me2-2,6)}(CH=NC6H3Me2-2,6),[10a] 11.16 ppm complexes 3b and 3c were determined by X-ray crystallo-
for ortho-C6H4{NH(C6H4Me-p)}(CH=NC6H3iPr2-2,6),[10a] graphic analysis. Crystals of ligands 2a and 2b suitable for
11.24 ppm for ortho-C6H4{NH(C6H4Me-p)}(CH=NC6H4- X-ray crystal structure determination were grown from
Me-p)[10a]] as a result of the electron-withdrawing properties ethyl acetate/petroleum ether at room temp. Crystals of
of the quinolyl group.
complexes 3b and 3c suitable for X-ray crystal structure de-
Scheme 1. Synthetic route for ligands 2a–2d and complexes 3a–3d.
Eur. J. Inorg. Chem. 2007, 4168–4175
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Q. Su, W. Gao, Q.-L. Wu, L. Ye, G.-H. Li, Y. Mu
FULL PAPER
termination were grown from n-hexane at room temp. The to the zinc center to form a six-membered chelating ring
ORTEP drawings of the molecular structures of 2a, 2b, 3b, that is nearly planar with the zinc atom lying 0.0371 Å (3b),
and 3c are shown in Figures 1 (top), 2, 3, and 4, respec- 0.0327 Å, and 0.0926 Å (3c) out of the plane. The imino
tively. Selected bond lengths and angles for 3b and 3c are C=N bond [1.277(7) Å for 3b] is slightly longer than that in
given in Table 1. The crystal packing [Figure 1 (bottom)] the free ligand after coordination to ZnII. The imino C=N
of 2a is consolidated by intramolecular N–H···N hydrogen bond in 3c [1.290(5) Å] is longer than that in 3b as a result
bonds and weak intermolecular C–H···N interactions of the increased steric hindrance of the isopropyl group rel-
[3.496(2) Å, 170.2°, (x, 1.5 – y, 0.5 + z)] arising from the
interactions between the nitrogen atom in the quinolyl ring
and the hydrogen atom of the imino CH=N to form an
infinite one-dimensional chain. There are no interactions
between each adjacent chain. X-ray analysis revealed that
the unit cell of 2b contains two independent molecules, one
of which is shown in Figure 2. There are intramolecular N–
H···N hydrogen bonds but no intermolecular C–H···N in-
teractions in the packing of 2b. The C=N bond lengths in
2a and 2b [1.271(2) Å for 2a, 1.267(4) and 1.275(4) Å for 2b]
are in the normal range.[11a] Complexes 3b and 3c belong to
the monoclinic space group C2/c and the triclinic space
¯
group P1, respectively. There is an n-hexane solvent mole-
cule in the unit cell of 3c. Both 3b and 3c exist in the di-
meric form with the nitrogen atom in the quinolyl ring co-
ordinating to the zinc atom in another molecule. As seen in
Figures 3 and 4, the zinc ions in both 3b and 3c adopt a
distorted tetrahedral geometry with the metal center coor-
dinated by an ethyl group, a quinolyl group, and the biden-
tate anilido–imine ligand. The anilido–imine ligand chelates
Figure 2. Molecular structure of compound 2b (all hydrogen atoms
and the other molecule have been omitted for clarity, and the ther-
mal ellipsoids are drawn at 30% probability levels).
Figure 3. Molecular structure of complex 3b (all hydrogen atoms
have been omitted for clarity, and the thermal ellipsoids are drawn
at 30% probability levels).
Figure 1. Top: Molecular structure of compound 2a. Bottom: The
packing of compound 2a (hydrogen bonds are indicated by dashed
lines and hydrogen atoms not involved in these interactions have
been omitted for clarity, and the thermal ellipsoids are drawn at
30% probability levels).
Figure 4. Molecular structure of complex 3c (all hydrogen atoms
and the n-hexane solvent molecule have been omitted for clarity,
and the thermal ellipsoids are drawn at 30% probability levels).
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Eur. J. Inorg. Chem. 2007, 4168–4175

Monoethylzinc Complexes with Anilido–Imine Ligands
ative to that of the ethyl group. The Zn–Nanilido distances lengths for complexes 3b [2.012(6) Å] and 3c [1.985(5) Å
[2.014(4) Å in 3b, 2.028(3) Å and 2.025(3) Å in 3c] are and 1.998(5) Å] are typical for such a bond[14] although
shorter than the Zn–Nimine distances [2.040(4) Å in 3b, slightly longer than that of similar [(C6H3iPr2)N=C(Me)
2.055(4) Å and 2.063(3) Å in 3c] owing to the formation of CH=C(Me)N(C6H3iPr2)]ZnEt (1.96 Å).[15] The Zn–Zn sep-
a polar (partially ionic) single bond from an electron-rich aration distances are 6.625 Å in 3b and 6.707 Å in 3c, which
anilido nitrogen atom to the ZnII center as opposed to a is indicative of no metal–metal interaction. The Nimine–Zn–
coordination bond in the latter case. The Zn–Nquinolyl dis- Nanilido bite angles are 92.63(16)° (in 3b), 92.33(14)° and
tances [2.313(4) Å in 3b, 2.290(4) Å and 2.266(3) Å in 3c] 93.38(14)° (in 3c), respectively. The dihedral angles between
are much longer than the Zn–Nimine distances, indicating the six-membered chelating ring and the phenyl ring at the
the weak coordination interaction between the zinc atom imine nitrogen are 80.7° (in 3b), 77.7° and 85.6° (in 3c),
and the nitrogen atom in the quinolyl ring. The Zn–C respectively. The dihedral angles between the six-membered
chelating ring and the quinolyl ring are 58.7° (in 3b), 59.9°
and 122.3° (in 3c), respectively.
Table 1. Selected bond lengths [Å] and angles [°] for 3b and 3c.[a]
Complex 3b
Fluorescent Properties
Zn1–N1
Zn1–N2
Zn1–C29
Zn1–N3#1
N1–C1
N2–C18
C29–Zn1–N1
C29–Zn1–N2
2.014(4)
2.040(4)
2.012(6)
2.313(4)
1.366(6)
1.277(7)
119.5(2)
127.1(2)
N1–Zn1–N2
92.63(16)
107.1(2)
112.90(16)
95.14(16)
114.0(3)
127.2(3)
123.0(4)
119.8(3)
C29–Zn1–N3#1
N1–Zn1–N3#1
N2–Zn1–N3#1
C7–N1–Zn1
C1–N1–Zn1
C18–N2–Zn1
C19–N2–Zn1
Table 2 summarizes the UV/Vis and fluorescent proper-
ties of compounds 2a–2d and 3a–3d determined in both
solution and the solid state. In solution, free ligands 2a–2d
all have a weak emission band at λ = 437, 437, 436, and
423 nm, respectively, whereas complexes 3a–3d in solution
show a stronger emission band (bandwidth at half-height =
77–79 nm) with λ = 573, 565, 555, and 515 nm, respectively
(Figure 5). The quantum yields of these complexes are rela-
tively low in solution. According to the literature,[6a,6b,10]
the observed luminescence of these complexes could be at-
tributed to π*–π transitions of their conjugated ligands. The
emission energies of these complexes are significantly red-
shifted relative to those of the free ligands, which could be
attributed to the fact that the coordination of the ligand to
the metal center lowers the energy gap between π* and π
of the ligand.[16] The emission energies of complexes 3a–3c
change in the order 3a Ͻ 3b Ͻ 3c, depending on the size of
the ortho-substituents of the rotatable aromatic ring at-
tached to the imine N atom that might affect the dihedral
angles between the aromatic ring and the six-membered
chelating ring and thus the extent of conjugation in these
complexes.[10a] The emission maxima of complexes 3a–3c
Complex 3c
Zn1–N2
Zn1–N3
Zn1–N4
Zn1–C61
N2–C12
N3–C18
N2–Zn1–N3
N2–Zn1–N4
N2–Zn1–C61
N3–Zn1–N4
N3–Zn1–C61
N4–Zn1–C61
C1–N2–Zn1
C12–N2–Zn1
C18–N3–Zn1
C19–N3–Zn1
2.028(3)
2.055(4)
2.290(4)
1.985(5)
1.353(5)
1.290(5)
92.33(14)
Zn2–N5
Zn2–N6
Zn2–N1
Zn2–C63
N5–C42
N6–C48
N5–Zn2–N6
2.025(3)
2.063(3)
2.266(3)
1.998(5)
1.361(5)
1.290(5)
93.38(14)
110.00(13)
117.21(19)
95.95(13)
121.79(18)
114.99(18)
114.7(3)
125.6(3)
121.5(3)
121.7(3)
112.36(13) N5–Zn2–N1
118.2(2)
96.08(14)
127.9(2)
107.7(2)
113.3(2)
127.5(3)
122.6(3)
119.7(3)
N5–Zn2–C63
N6–Zn2–N1
N6–Zn2–C63
N1–Zn2–C63
C31–N5–Zn2
C42–N5–Zn2
C48–N6–Zn2
C49–N6–Zn2
[a] Symmetry transformations used to generate equivalent atoms:
#1: –x, y, –z + 0.5.
Table 2. Optical properties of ligands 2a–2d and complexes 3a–3d in n-hexane and the solid state.
Compound
Absorption
Emission
λ [nm]
Quantum yields[a]
Conditions (at T = 298 K)
[nm] (ε [dm3 mol–1 cm–1])
φ
2a
2b
2c
2d
3a
3b
3c
3d
386 (14713)
383 (20480)
384 (23431)
372 (14253)
476 (11319)
472 (24198)
466 (22475)
454 (12176)
437
468
437
468
436
467
423
436
573
583
565
561
555
553
515
523
0.002
0.002
0.003
0.015
0.042
0.048
0.087
0.070
n-hexane
solid
n-hexane
solid
n-hexane
solid
n-hexane
solid
n-hexane
solid
n-hexane
solid
n-hexane
solid
n-hexane
solid
[a] Determined by using quinine sulfate in 0.1  sulfuric acid as a standard.
Eur. J. Inorg. Chem. 2007, 4168–4175
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FULL PAPER
distilled under an atmosphere of argon prior to use. C6D6 was dried
with activated 4 Å molecular sieves and vacuum-transferred to a
sodium-mirrored air-free flask. CDCl3 was dried with CaH2 for
48 h and vacuum-transferred to an air-free flask. ZnEt2 and nBuLi
were purchased from Aldrich and used as received. ortho-
C6H4F(CH=NC6H3Me2-2,6) (1a) and ortho-C6H4F(CH=NC6H3-
iPr2-2,6) (1c) were synthesized according to literature proce-
dures.[11] 7-Amino-2,4-dimethylquinoline was synthesized accord-
are redshifted by about 40–58 nm relative to the emission
maximum of complex 3d because of the larger conjugated
quinolyl ring in 3a–3c. All complexes 3a–3d emit bright
fluorescence in the solid state upon irradiation with an ade-
quate excitation wavelength. The emission spectra of com-
plexes 3a–3d in the solid state are shown in Figure 6. Com-
plexes 3a–3d have a relatively narrow band (bandwidth at
half-height = 72, 64, 55, and 60 nm) in the solid state with
λ = 583, 561, 553, and 523 nm, respectively. It seemed that
ing to
(NHC6H3Me2-2,6)(CH=NC6H3iPr2-2,6) (2d) was synthesized ac-
a
literature procedure.[17] The ligand ortho-C6H4-
the coordination number of zinc does not play a role in the cording to a literature method.[12] 1H and 13C NMR spectra were
measured with a Varian Mercury-300 or Bruker AVANCE-500
NMR spectrometer. Elemental analyses were performed with a
Perkin–Elmer 2400 analyzer. UV/Vis absorption spectra were re-
corded with an UV-3100 spectrophotometer. Fluorescent measure-
ments were carried out with an RF-5301PC.
fluorescence. The emission maxima of complexes 3b and 3c
in the solid state are slightly blueshifted relative to their
corresponding emission maxima in solution; this may be
due to the reduced conjugation of the two complexes, as
the free rotation of the aryl rings in these complexes is
blocked in the solid state. The emission maxima of com- ortho-C6H4F(CH=NC6H3Et2-2,6) (1b): A mixture of ortho-fluoro-
benzaldehyde (4.00 mL, 37.7 mmol), 2,6-diethylaniline (6.20 mL,
37.7 mmol), and anhydrous MgSO4 (1 g) in n-hexane (40 mL) was
stirred at room temp. for 2 h. The mixture was filtered, and the
solvents were evaporated to dryness to give the product as salmon
pink oil. The crude product was purified by reduced-pressure distil-
lation. Yield: 6.0 g, 62%. 1H NMR (500 MHz, CDCl3, 298 K): δ =
1.16 (t, J = 7.5 Hz, 2ϫ3 H, CH2CH3), 2.51 (q, J = 7.5 Hz, 2ϫ2
H, CH2CH3), 7.06 (d, J = 6.5 Hz, 1 H), 7.11 (d, J = 7.5 Hz, 2 H),
7.16 (t, J = 9.5 Hz, 1 H), 7.29 (t, J = 7.5 Hz, 1 H), 7.50 (q, J =
7.5 Hz, 1 H), 8.25 (t, J = 7.5 Hz, 1 H), 8.55 (s, 1 H, CH=N) ppm.
13C{1H} NMR (125.1 MHz, CDCl3, 298 K): δ = 15.1 (CH2CH3),
plexes 3a and 3d in the solid state show a redshift relative
to their corresponding emission maximum in solution,
which is normally observed for most fluorescent com-
pounds in the solid state probably owing to π–π stacking of
aromatic rings in the molecules.[6b]
2
25.1 (CH2CH3), 116.3 (d, JC,F = 21 Hz), 124.2 (quaternary aro-
3
4
matic), 124.6, 124.9 (d, JC,F = 3.5 Hz), 126.7, 128.1 (d, JC,F
=
3
2.6 Hz), 133.4 (d, JC,F = 8.5 Hz), 133.5 (quaternary aromatic),
3
150.8 (quaternary aromatic), 156.1 (d, JC,F = 4.8 Hz, CH=N),
163.2 (d, 1JC,F = 253.5 Hz, CF) ppm. C17H18FN (255.33): calcd. C
79.97, H 7.11, N 5.49; found C 79.89, H 7.20, N 5.56.
ortho-C6H4{7-NH(2,4-Me2)C9H4N}(CH=NC6H3Me2-2,6) (2a): A
solution of nBuLi (1.60 , 22.5 mmol) in n-hexane was added to a
solution of 7-amino-2,4-dimethylquinoline (3.89 g, 22.5 mmol) in
THF (30 mL) at –78 °C. The mixture was warmed to room temp.
and stirred overnight. The resulting solution was transferred into a
solution of ortho-C6H4F(CH=NC6H3Me2-2,6) (5.09 g, 22.5 mmol)
in THF (30 mL) at 25 °C. After stirring for 2 d, the reaction was
quenched with H2O (20 mL). The organic phase was evaporated to
dryness to give the crude product as a brown oil that was purified
by column chromatography on silica gel (ethyl acetate/petroleum
ether, 1:5) to give the pure product as yellowish crystals (3.5 g,
41%). 1H NMR (300 MHz, CDCl3, 298 K): δ = 2.21 (s, 2ϫ3 H,
CH3), 2.65 (s, 3 H, quinolyl-CH3), 2.72 (s, 3 H, quinolyl-CH3), 6.93
(t, J = 7.5 Hz, 1 H, Ph-H), 6.98–7.03 (m, 2 H, Ph-H and quinolyl-
H), 7.11–7.13 (d, 2 H, Ph-H), 7.33–7.42 (m, 3 H, Ph-H and quino-
lyl-H), 7.81 (d, J = 8.4 Hz, 1 H, Ph-H), 7.86 (d, J = 9.3 Hz, 1 H,
Ph-H), 8.03 (s, 1 H, quinolyl-H), 8.36 (s, 1 H, CH=NAr), 11.64 (s,
1 H, quinolyl-NH) ppm. 13C{1H} NMR (75.4 MHz, CDCl3,
298 K): δ = 18.5 (CH3), 18.6 (CH3), 24.9 (quinolyl-CH3), 114.3,
114.9, 118.3, 119.0, 121.0, 121.2, 122.4, 124.1, 124.7, 127.8, 128.2,
132.1, 134.8, 142.4, 144.3, 144.8, 148.7, 150.1, 158.9, 165.8 (CH=N)
ppm. C26H25N3 (379.50): calcd. C 82.29, H 6.64, N 11.07; found C
82.21, H 6.70, N 11.02.
Figure 5. Emission spectra of complexes 3a–3d in n-hexane.
Figure 6. Emission spectra of complexes 3a–3d in the solid state.
Experimental Section
ortho-C6H4{7-NH(2,4-Me2)C9H4N}(CH=NC6H3Et2-2,6) (2b):
A
General: All organometallic reactions were performed by using
standard Schlenk techniques under an atmosphere of high-purity
argon or by using glove box techniques. Toluene, n-hexane, and
THF were dried by refluxing over sodium and benzophenone and
solution of nBuLi (1.60 , 12.8 mmol) in n-hexane was added to a
solution of 7-amino-2,4-dimethylquinoline (2.20 g, 12.8 mmol) in
THF (20 mL) at –78 °C. The mixture was warmed to room temp.
and stirred overnight. The resulting solution was transferred into a
4172
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 4168–4175

Monoethylzinc Complexes with Anilido–Imine Ligands
solution of ortho-C6H4F(CH=NC6H3Et2-2,6) (3.29 g, 12.8 mmol)
in THF (30 mL) at 25 °C. After stirring for 2 d, the reaction was
quenched with H2O (20 mL). The organic phase was evaporated to
dryness to give the crude product as a dark brown oil that was
purified by column chromatography on silica gel (ethyl acetate/pe-
ortho-C6H4[7-N(2,4-Me2)C9H4N](CH=NC6H3Et2-2,6)ZnEt (3b): A
solution of ortho-C6H4{7-NH(2,4-Me2)C9H4N}(CH=NC6H3Et2-2,6)
(0.19 g, 0.47 mmol) in toluene (20 mL) was slowly added to a solu-
tion of ZnEt2 (0.47 mmol) in toluene (10 mL) at room temp. with
stirring. The mixture was stirred at room temp. for 1 h and at 90 °C
troleum ether, 1:3) to give the pure product as yellowish crystals for an additional 3 h. The solvent was removed in vacuo, and the
1
(2.20 g, 43%). H NMR (300 MHz, CDCl3, 298 K): δ = 1.16 (t, J obtained orange-red residue was recrystallized from n-hexane
= 7.8 Hz, 2ϫ3 H, CH3CH2), 2.57 (q, J = 7.8 Hz, 2ϫ2 H,
CH3CH2), 2.64 (s, 3 H, quinolyl-CH3), 2.70 (s, 3 H, quinolyl-CH3),
6.92 (t, J = 7.5 Hz, 1 H, Ph-H), 7.01 (s, 1 H, quinolyl-H), 7.06–
7.16 (m, 3 H, Ph-H), 7.32 (dd, J = 8.7, 2.4 Hz, 1 H, quinolyl-H),
7.38–7.43 (m, 2 H, Ph-H and quinolyl-H), 7.82 (d, J = 9.0 Hz, 1
H, Ph-H), 7.87 (d, J = 9.0 Hz, 1 H, Ph-H), 8.07 (s, 1 H, quinolyl-
H), 8.37 (s, 1 H, CH=NAr), 11.62 (s, 1 H, quinolyl-NH) ppm.
13C{1H} NMR (75.4 MHz, CDCl3, 298 K): δ = 14.8 (CH2CH3),
(10 mL) to give orange-red crystals (0.19 g, 82%). 1H NMR
(500 MHz, C6D6, 298 K):
δ = 0.63 (q, J = 8.0 Hz, 2 H,
ZnCH2CH3), 1.09 (t, J = 7.5 Hz, 2ϫ3 H, CH2CH3), 1.22 (t, J =
8.0 Hz, 3 H, ZnCH2CH3), 2.30 (s, 3 H, quinolyl-CH3), 2.43–2.52
(m, 2ϫ2 H, CH2CH3), 2.63 (s, 3 H, quinolyl-CH3), 6.57 (t, J =
7.5 Hz, 1 H, Ph-H), 6.70 (s, 1 H), 7.04–7.10 (m, 4 H), 7.15 (t, J =
8.0 Hz, 1 H), 7.29 (t, J = 9.0 Hz, 1 H), 7.57 (d, J = 9.0 Hz, 1 H),
7.76 (d, J = 9.0 Hz, 1 H), 7.92 (s, 1 H), 8.47 (s, 1 H, CH=N) ppm.
18.4 (quinolyl-CH3), 24.9 (CH3CH2), 25.0 (quinolyl-CH3), 114.2, 13C{1H} NMR (125.1 MHz, C6D6, 298 K): δ = –1.8 (ZnCH2CH3),
115.0, 118.3, 118.9, 121.0, 121.3, 122.4, 124.4, 124.7, 126.4, 132.1, 12.0 (ZnCH2CH3), 14.5 (CH2CH3), 17.9 (quinolyl-CH3), 25.0 (qui-
133.7, 134.9, 142.3, 144.2, 144.8, 148.5, 149.4, 158.9, 165.6 (CH=N) nolyl-CH3 and CH2CH3), 114.3, 115.9, 117.3, 121.3, 123.7, 124.5,
ppm. C28H29N3 (407.55): calcd. C 82.52, H 7.17, N 10.31; found C
82.59, H 7.21, N 10.20.
124.6, 125.5, 126.3, 126.6, 134.6, 135.9, 137.6, 142.9, 148.1, 150.5,
151.8, 157.4, 158.7, 170.0 (CH=N) ppm. C60H66N6Zn2 (1001.98):
calcd. C 71.92, H 6.64, N 8.39; found C 71.85, H 6.58, N 8.50.
ortho-C6H4{7-NH(2,4-Me2)C9H4N}(CH=NC6H3iPr2-2,6) (2c): A
solution of nBuLi (1.60 , 14.4 mmol) in n-hexane was added to a
solution of 7-amino-2,4-dimethylquinoline (2.50 g, 14.4 mmol) in
THF (30 mL) at –78 °C. The mixture was warmed to room temp.
and stirred overnight. The resulting solution of LiNHAr [Ar = 7-
ortho-C6H4{7-N(2,4-Me2)C9H4N}(CH=NC6H3iPr2-2,6)ZnEt (3c):
A solution of ortho-C6H4{7-NH(2,4-Me2)C9H4N}(CH=NC6H3iPr2-
2,6) (0.20 g, 0.55 mmol) in toluene (20 mL) was slowly added to a
solution of ZnEt2 (0.55 mmol) in toluene (10 mL) at room temp.
with stirring. The mixture was stirred at room temp. for 1 h and at
(2,4-Me2)C9H4N] was transferred into
a solution of ortho-
C6H4F(CH=NC6H3iPr2-2,6) (4.10 g, 14.4 mmol) in THF (30 mL) 90 °C for an additional 3 h. The solvent was removed in vacuo, and
at 25 °C. After stirring for 2 d, the reaction was quenched with
H2O (20 mL). The organic phase was evaporated to dryness to give
the crude product as a dark brown oil that was recrystallized from
methanol to give the pure product as yellow solid (3.01 g, 48%).
the obtained orange-red residue was recrystallized from n-hexane
(10 mL) to give orange-red crystals (0.25 g, 84%). 1H NMR
(300 MHz, C6D6, 298 K):
ZnCH2CH3), 0.99 [d, J = 6.6 Hz, 6 H, CH(CH3)2], 1.05 [dd, J =
H, CH(CH3)2], 1.16 (t, 8.1 Hz, H,
H, CH(CH3)2], 2.63 (s, 3 H, quinolyl-CH3), 2.68 (s, 3 H, quinolyl- ZnCH2CH3), 2.15 (s, 3 H, quinolyl-CH3), 2.49 (s, 3 H, quinolyl-
δ = 0.56 (q, J = 8.1 Hz, 2 H,
1H NMR (300 MHz, CDCl3, 298 K): δ = 1.19 [d, J = 6.5 Hz, 12 18.3, 6.9 Hz,
6
J
=
3
CH3), 3.05 [sept, J = 6.5 Hz, 2 H, CH(CH3)2], 6.97 (t, J = 7.5 Hz,
1 H, Ph-H), 7.01 (s, 1 H, quinolyl-H), 7.17–7.22 (m, 3 H, Ph-H
CH3), 2.97 [sept, J = 6.9 Hz, 2ϫ1 H, CH(CH3)2], 6.44 (t, J =
8.1 Hz, 1 H, Ph-H), 6.55 (s, 1 H, quinolyl-H), 6.94–6.99 (m, 2ϫ1
and quinolyl-H), 7.31–7.43 (m, 3 H, Ph-H and quinolyl-H), 7.81– H, Ph-H), 7.03–7.10 (m, 3ϫ1 H, Ph-H), 7.49 (dd, J = 8.7, 2.1 Hz,
7.88 (m, 2 H, Ph-H), 8.04 (s, 1 H, quinolyl-H), 8.35 (s, 1 H, 1 H, quinolyl-H), 7.62 (d, J = 8.7 Hz, 1 H, quinolyl-H), 7.97 (s, 1 H,
CH=NAr), 11.59 (s, 1 H, quinolyl-NH) ppm. 13C{1H} NMR quinolyl-H), 8.41 (s, 1 H, CH=N) ppm. 13C{1H} NMR (75.4 MHz,
(75.4 MHz, CDCl3, 298 K): 18.5 (quinolyl-CH3), 23.5 C6D6, 298 K): δ = –1.3 (ZnCH2CH3), 12.4 (ZnCH2CH3), 18.2 (qui-
[CH(CH3)2], 25.0 (quinolyl-CH3), 28.1 [CH(CH3)2], 114.3, 115.1, nolyl-CH3), 24.4 [CH(CH3)2], 25.2 (quinolyl-CH3), 28.8 [CH-
δ
=
118.3, 118.9, 121.0, 121.3, 122.5, 123.1, 124.6, 124.7, 132.2, 135.0,
138.1, 142.3, 144.2, 144.9, 148.3, 149.0, 159.0, 165.7 (CH=N) ppm.
(CH3)2], 114.6, 116.1, 117.4, 121.6, 123.8, 123.9, 124.6, 124.9, 125.7,
127.0, 134.9, 138.0, 140.9, 143.3, 146.9, 150.6, 152.1, 157.6, 159.0,
C30H33N3 (435.60): calcd. C 82.72, H 7.64, N 9.65; found C 82.82, 170.2 (CH=N) ppm. C64H74N6Zn2·C6H14 (1144.20): calcd. C 73.47,
H 7.70, N 9.51.
H 7.75, N 7.34; found C 73.36, H 7.81, N 7.16.
ortho-C6H4{7-N(2,4-Me2)C9H4N}(CH=NC6H3Me2-2,6)ZnEt (3a):
A solution of ortho-C6H4{7-NH(2,4-Me2)C9H4N}(CH=NC6H3-
Me2-2,6) (0.19 g, 0.50 mmol) in toluene (20 mL) was slowly added
to a solution of ZnEt2 (0.50 mmol) in toluene (10 mL) at room
temp. with stirring. The mixture was stirred at room temp. for 1 h
and at 90 °C for an additional 3 h. The solvent was removed in
vacuo, and the obtained orange-red residue was recrystallized from
n-hexane (10 mL) to give an orange-red solid (0.18 g, 78%). 1H
NMR (300 MHz, C6D6, 298 K): δ = 0.55 (q, J = 7.8 Hz, 2 H,
ortho-C6H4(NC6H3Me2-2,6)(CH=NC6H3iPr2-2,6)ZnEt (3d):
A
solution of ortho-C6H4(NHC6H3Me2-2,6)(CH=NC6H3iPr2-2,6)
(0.28 g, 0.72 mmol) in toluene (20 mL)was slowly added to a solu-
tion of ZnEt2 (0.72 mmol) in toluene (10 mL) at room temp. with
stirring. The mixture was stirred at room temp. for 1 h and at 90 °C
for an additional 3 h. The solvent was removed in vacuo, and the
obtained yellow-green residue was recrystallized from n-hexane
1
(10 mL) to give a yellow solid (0.25 g, 85%). H NMR (300 MHz,
CDCl3, 298 K): δ = 0.02 (q, J = 8.1 Hz, 2 H, ZnCH2CH3), 0.70 (t,
ZnCH2CH3), 1.16 (t, J = 7.8 Hz, 3 H, ZnCH2CH3), 1.95 (s, 2ϫ3 J = 8.1 Hz, 3 H, ZnCH2CH3), 1.27 [d, J = 6.6 Hz, 4ϫ3 H,
H, CH3), 2.23 (s, 3 H, quinolyl-CH3), 2.60 (s, 3 H, quinolyl-CH3), CH(CH3)2], 2.23 (s, 2ϫ3 H, CH3), 3.10 [sept, J = 6.6 Hz, 2ϫ1 H,
6.51 (t, J = 7.8 Hz, 1 H, Ph-H), 6.63 (s, 1 H), 6.94–7.05 (m, 6 H),
7.49 (d, J = 8.4 Hz, 1 H), 7.70 (s, 2 H), 8.40 (s, 1 H, CH=N) ppm.
13C{1H} NMR (75.4 MHz, C6D6, 298 K): δ = –1.2 (ZnCH2CH3),
12.2 (ZnCH2CH3), 18.2 (quinolyl-CH3), 18.5 (CH3), 25.2 (quinolyl-
CH(CH3)2], 6.38 (d, J = 9.0 Hz, 1 H), 6.56 (t, J = 6.9 Hz, 1 H),
7.15–7.32 (m, 8 H), 8.29 (s, 1 H, CH=N) ppm. 13C{1H} NMR
(75.4 MHz, CDCl3, 298 K):
δ = –2.9 (ZnCH2CH3), 11.3
(ZnCH2CH3), 18.3 (CH3), 24.1 [CH(CH3)2], 28.5 [CH(CH3)2],
CH3), 114.4, 116.3, 117.5, 121.5, 124.6, 124.9, 125.7, 126.0, 128.7, 113.0, 114.2, 115.1, 123.5, 124.2, 126.5, 128.5, 133.1, 134.7, 137.6,
130.1, 134.7, 138.0, 143.2, 149.3, 150.6, 152.1, 157.5, 159.0, 170.2 140.5, 146.6, 147.3, 156.4, 169.5 (CH=N) ppm. C29H36N2Zn
(CH=N) ppm.C56H58N6Zn2 (945.88): calcd. C 71.11, H 6.18, N (478.00): calcd. C 72.87, H 7.59, N 5.86; found C 72.71, H 7.68, N
8.88; found C 71.22, H 6.14, N 8.75.
5.75.
Eur. J. Inorg. Chem. 2007, 4168–4175
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4173

Q. Su, W. Gao, Q.-L. Wu, L. Ye, G.-H. Li, Y. Mu
FULL PAPER
X-ray Structure Determinations of 2a, 2b, 3b, and 3c: Single crystals
of 2a and 2b suitable for X-ray structural analysis were obtained
from ethyl acetate/petroleum ether at room temp. Single crystals of
n-hexane at room temp. Diffraction data were collected at 293 K
with a Rigaku R-AXIS RAPID IP diffractometer equipped with
graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å) for all
3b and 3c suitable for X-ray structural analysis were obtained from compounds. The structures were solved by direct methods[18] and
refined by full-matrix least-squares on F2. All non-hydrogen atoms
were refined anisotropically and the hydrogen atoms were included
in idealized position. All calculations were performed by using the
Table 3. Crystal data and structural refinement details for 2a and 2b.
SHELXTL[19] crystallographic software packages. Details of the
crystal data, data collections, and structure refinements are summa-
rized in Tables 3 (2a and 2b) and 4 (3b and 3c). CCDC-636086 (for
2a), -636087 (for 2b), -636088 (for 3b), and -636089 (for 3c) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
2a
2b
Empirical formula
Formula mass
Temperature [K]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C26H25N3
379.49
293(2)
monoclinic
P21/c
17.371(4)
8.4558(17)
15.347(3)
90
107.62(3)
90
2148.5(7)
4
C28H29N3
407.54
293(2)
triclinic
¯
P1
9.989(2)
13.204(3)
18.038(4)
75.85(3)
87.79(3)
88.84(3)
2305.1(8)
4[a]
Acknowledgments
γ [°]
Volume [Å3]
Z
This work was supported by the National Natural Science Founda-
tion of China (No. 20674024) and Ministry of Science and Technol-
ogy of China (No. 2002CB6134003).
Dcalcd. [Mgm–3]
F(000)
1.173
808
1.174
872
θ range for data collection [°] 3.11–27.48
3.01–27.48
–12ՅhՅ12
–17ՅkՅ17
–23ՅlՅ23
10002/30/568
1.029
Limiting indices
–22ՅhՅ20
–10ՅkՅ10
–19ՅlՅ19
4864/0/271
1.026
[1] a) Y. Hamada, T. Sano, H. Fujii, Y. Nishino, K. Shibata, Jpn.
J. Appl. Phys. 1996, 35, L1339–L1341; b) H. Tanaka, S. Tokito,
Y. Taga, A. Okada, J. Mater. Chem. 1998, 8, 1999–2003 and
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Shuai, D. B. Zhu, J. Am. Chem. Soc. 2003, 125, 14186–14824.
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Shibata, Jpn. J. Appl. Phys. 1993, 32, L511–L513; b) T. Sano,
Y. Nishio, Y. Hamada, H. Takahashi, T. Usuki, K. Shibata, J.
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Lin, Dalton Trans. 2004, 1731–1738.
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [IϾ2σ(I)]
[b]
[b]
R1 = 0.0546
R1 = 0.0816
[c]
[c]
wR2 = 0.1200 wR2 = 0.2028
[b]
[b]
R indices (all data)
R1 = 0.1054
R1 = 0.1636
[c]
[c]
wR2 = 0.1393 wR2 = 0.2450
Largest diff. peak/hole [eA–3] 0.152/–0.138
0.374/–0.315
[a] There are two crystallographically independent molecules in the
2
asymmetric unit. [b] R1 = ∑||Fo| – |Fc||/∑|Fo|. [c] wR2 = {∑[w (Fo
–
2 2
Fc ) ]/∑[w (Fo2)2]}1/2
.
Table 4. Crystal data and structural refinement details for 3b and 3c.
3b
3c
Empirical formula
Formula mass
Temperature [K]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
a [°]
β [°]
C60H66N6Zn2
1001.93
293(2)
monoclinic
C2/c
25.656(5)
17.437(4)
17.348(4)
90
129.37(3)
90
C70H88N6Zn2
1144.20
293(2)
triclinic
¯
P1
13.538(3)
15.539(3)
16.885(3)
105.85(3)
108.94(3)
96.33(3)
3153.8(11)
2
[4] Y. Hamada, T. Sano, H. Fujii, Y. Nishino, H. Takahashi, K.
Shibata, Appl. Phys. 1997, 71, 3338–3340.
[5] a) K. Y. Ho, W. Y. Yu, K. K. Cheung, C. M. Che, Chem. Com-
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C. M. Che, J. Chem. Soc. Dalton Trans. 1999, 1581–1586.
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Wang, Inorg. Chem. 2000, 39, 2397–2404; b) Q. G. Wu, J. A.
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5248–5254; c) L. V. Sazanovich, C. Kirmarier, E. Hinclin, L.
Yu, D. F. Bocian, J. S. Lindsey, D. Holten, J. Am. Chem. Soc.
2004, 126, 2664–2665; d) Y. J. Kang, C. Seward, D. T. Song,
S. N. Wang, Inorg. Chem. 2003, 42, 2789–2797; e) W. Y. Wong,
K. Y. Tsang, K. H. Tam, G. L. Lu, C. Sun, J. Organomet.
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J. Chem. 2002, 26, 1365–1370; g) S. N. Wang, Coord. Chem.
Rev. 2001, 215, 79–98.
γ [°]
Volume [Å3]
Z
5999(2)
4
1.109
Dcalcd. [Mgm–3]
F(000)
1.205
1220
2112
θ range for data collection [°] 3.04–27.48
3.03–27.48
–17ՅhՅ16
–20ՅkՅ20
–21ՅlՅ21
13686/5/719
0.996
Limiting indices
–33ՅhՅ33
–22ՅkՅ22
–18ՅlՅ22
6726/0/289
1.021
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [IϾ2σ(I)]
[a]
[a]
R1 = 0.0811
R1 = 0.0621
[b]
[b]
wR2 = 0.1988 wR2 = 0.1668
[7] V. W.-W. Yam, Y.-L. Pui, K.-K. Cheung, Inorg. Chem. 2000,
39, 5741–5746.
[8] a) C.-F. Lee, K.-F. Chin, S.-M. Peng, C.-M. Che, J. Chem. Soc.
Dalton Trans. 1993, 467–470; b) Y. G. Ma, H.-Y. Chao, Y. Wu,
S. T. Lee, W.-Y. Yu, C.-M. Che, Chem. Commun. 1998, 2491–
[a]
[a]
R indices (all data)
R1 = 0.1565
R1 = 0.1243
[b]
[b]
wR2 = 0.2430 wR2 = 0.2109
Largest diff. peak/hole [eA–3] 0.981/–1.248
[a] R1 = ∑||Fo| – |Fc||/∑|Fo|. [b] wR2 = {∑[w (Fo2 – Fc2)2]/∑[w (Fo2)2]}1/2
0.576/–0.436
.
4174
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 4168–4175

Monoethylzinc Complexes with Anilido–Imine Ligands
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Received: February 8, 2007
Published Online: July 12, 2007
Eur. J. Inorg. Chem. 2007, 4168–4175
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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