A bifunctional diketimine ligand for secondary building blocks: Formation of a 2D copper-zinc coordination polymer

Article abstract of DOI:10.1002/ejic.201000903

Condensation of 3-(aminomethyl)pyridine with acetylacetone in the presence of 2 equiv. of HCl affordedN,Na'-bis(3-pyridylmethyl)-2-amino-4-imino-pent-2- ene, nacnac^CH2PyH, a diketimine with pendant pyridine donors.Under the same conditions, 2- and 4-(aminomethyl)pyridine afforded the respective 1-(2-pyridyl)- and 1-(4-pyridyl)-2,4-dimethylpyrrol. The heteroleptic complex (nacnac^CH2Py)(nacnac^Bn)Zn was obtained upon reaction of nacnac^CH2PyH with nacnac^BnZnEt. Combining 2 equiv. of this ligand with ZnEt₂ afforded the homoleptic complex nacnac ^CH2Py₂Zn. The latter forms a 2D coordination polymer upon reaction with [Cu(NCMe)₄][PF₆], which shows short-lived luminescence at ambient temperature. The coordination polymer and complex (nacnac^CH2Py)(nacnac^Bn)Zn were characterised by single-crystal X-ray diffraction. Zinc complexes of a new bifunctional diketimine ligand with pendant pyridine donor ligands can serve as building blocks for polynuclear or supramolecular assemblies.Reaction of the building block with Cu^I cations affords a bimetallic, luminescent Cu-Zn coordination polymer. Copyright

Full text of DOI:10.1002/ejic.201000903

FULL PAPER
DOI: 10.1002/ejic.201000903
A Bifunctional Diketimine Ligand for Secondary Building Blocks: Formation
of a 2D Copper–Zinc Coordination Polymer
Élodie Rousset,[a] Todd J. J. Whitehorne,[a] Valérie Baslon,[a] Christian Reber,[a] and
Frank Schaper*[a]
Keywords: Zinc / Copper / Coordination polymers / Luminescence / Bifunctional ligands / Diketimines
Condensation of 3-(aminomethyl)pyridine with acetyl- nacnacBnZnEt. Combining 2 equiv. of this ligand with ZnEt2
acetone in the presence of 2 equiv. of HCl afforded
N,NЈ-bis(3-pyridylmethyl)-2-amino-4-imino-pent-2-ene, nac-
nacCH2PyH, a diketimine with pendant pyridine donors.
Under the same conditions, 2- and 4-(aminomethyl)pyridine
afforded the respective 1-(2-pyridyl)- and 1-(4-pyridyl)-2,4-
dimethylpyrrol. The heteroleptic complex (nacnacCH2Py)(nac-
nacBn)Zn was obtained upon reaction of nacnacCH2PyH with
afforded the homoleptic complex nacnacCH2Py2Zn. The latter
forms
a 2D coordination polymer upon reaction with
[Cu(NCMe)4][PF6], which shows short-lived luminescence at
ambient temperature. The coordination polymer and com-
plex (nacnacCH2Py)(nacnacBn)Zn were characterised by sin-
gle-crystal X-ray diffraction.
Introduction
The preparation of secondary building blocks for the
construction of metal–organic frameworks[1] or polynuclear
complexes[2] requires bifunctional ligands that form geo-
metrically and chemically inert metal complexes with pen-
dant donor substituents for further supramolecular as-
sembly. In the course of our recent investigations into the
coordination chemistry of N-alkyl-substituted β-diketimine
ligands (nacnacR), we found that they form (in contrast to
their N-aryl counterparts) highly symmetric homoleptic
bis(diketiminate) complexes nacnacR2M with tetrahedral
(Zn, Mg)[3,4] or square-planar (Cr)[5,6] geometry. We thus
undertook to introduce pendant donor groups into the di-
ketiminate framework and to investigate their potential as
secondary building blocks. These ligands would contain a
chelating anionic coordination site, which would be respon-
sible for the formation of the geometrically inert building
block, and secondary coordination sites, which allow the
extension of the building block into defined or infinite poly-
nuclear assemblies (Figure 1).
Figure 1. Bis(diketiminate) complexes as secondary building
blocks.
MLCT transitions) as central metals, there are few reports
of luminescent coordination polymers that combine both
metals.[8]
Here we report the preparation of nacnacCH2Py2Zn and
its coordination polymer with CuI. Coordination polymers
or metal–organic frameworks have attracted interest as
solid-state materials for luminescence applications.[7] While
luminescent coordination polymers have been reported with
zinc(II) (mostly LMCT transitions) or copper(I) (mostly
Results and Discussion
Ligand and Complex Synthesis
N-Alkyl-substituted β-diketimines can be prepared by
simple condensation of acetylacetone with 2 equiv. of amine
in the presence of 1 equiv. of acid (HCl or TsOH) and azeo-
tropic removal of water.[9] Reaction of 3-(aminomethyl)pyr-
idine with acetylacetone under these conditions afforded,
however, only the monocondensation product acnacCH2Py
(Scheme 1), which was identified by independent synthesis.
In the presence of 2 equiv. of HCl, ligand 1 could be pre-
pared in 40–55% yield. Further increase of the acid concen-
[a] Département chimie, Université de Montréal, Montréal,
Québec, H3C 3J7, Canada
E-mail: Frank.Schaper@umontreal.ca
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201000903.
Eur. J. Inorg. Chem. 2011, 331–335
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
331

É. Rousset, T. J. J. Whitehorne, V. Baslon, C. Reber, F. Schaper
FULL PAPER
Scheme 1.
tration did not affect the reaction outcome. When 2- and 4- however, unable to obtain X-ray quality crystals from these
(aminomethyl)pyridine are reacted under the same condi- reactions. On the other hand, slow diffusion of [Cu-
tions, 1-(2-pyridyl)- and 1-(4-pyridyl)-2,4-dimethylpyrrol, (NCMe)4][PF6] in acetonitrile into a solution of 2 in toluene
respectively, were obtained, most likely due to the more ac- cleanly afforded yellow crystals of the heterometallic coor-
cessible enimine tautomer in those compounds (Scheme 1). dination polymer [2Cu]n[PF6]n (4).
Preparation of pyrrols from acetylacetone and 2- or 4-(ami-
nomethyl)pyridine has been reported before, albeit under
slightly more forcing conditions.[10]
Crystal Structures
Reaction of 2 equiv. of 1 with diethylzinc generated the
homoleptic complex nacnacCH2Py2Zn (2) (Scheme 2). A het-
eroleptic complex could be obtained by stepwise reaction,
and addition of 1 to nacnacBnZnEt afforded (nacnacCH2Py)-
(nacnacBn)Zn, 3. Compounds 1 and 2 were obtained in high
yields as slightly coloured oils, which show no or only very
minor impurities in 1H NMR, and could be further purified
by crystallisation if desired. In crystalline form 2 could be
handled in air for short times. Complex 3 did not show any
signs of decomposition after heating to reflux in C6D6 for
several hours. Only one singlet is observed for the CH2
Apart from minor differences in unit cell parameters and
torsion angles, the crystal structure of 3 (Figure 2, Table 1)
is isostructural to that of the homoleptic complex nac-
1
group in H NMR spectra of 2 and two singlets for the
CH2Py and CH2Ph groups in 3, indicating that rotations
around the N–CH2 and CH2–Ar bonds are fast on the
NMR time scale.
Figure 2. X-ray structure of 3. Hydrogen atoms are omitted for
clarity. Thermal ellipsoids are drawn at the 50% probability level.
Table 1. Bond lengths [Å] and angles [°] in the X-ray structures of
complex 3 and coordination polymer 4.
3
4
nacnacBn2Zn[3]
Zn1–N
1.988(2),
1.991(2)
1.982(2)–1.991(2)
1.983(1),
1.989(1)
Cu1–N
2.048(2)–2.136(2)
97.54(7), 97.91(7)
Scheme 2.
N–Zn1–N[a]
97.71(11),
98.49(11)
97.93(7),
98.27(7)
To test for the ability of 2 to act as a secondary building
block, we investigated its reactions with metal complexes
containing labile ligands. Reaction of 2 with PdCl2-
(NCPh)2 in various ratios, concentrations and temperatures
consistently yielded brown precipitates, most likely a coor-
N–Cu1–N
97.25(7)–135.22(8)
89
66–74
nacnac-nacnac[b]
nacnac-Ph[c]
89
71, 73
89
69, 88
[a] Diketiminate bite angle. [b] Angle between the mean planes of
diketiminate ligands. [c] Angles between the mean planes of Ph
dination polymer containing trans-Py2PdCl2 units. We were, substituents and the respective diketiminate ligand.
332 Eur. J. Inorg. Chem. 2011, 331–335
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Formation of a 2D Copper–Zinc Coordination Polymer
Figure 3. Repeating unit of coordination polymer 4 (pyridyl ligands at Cu1 and Cu1A-Cu1C added for clarity). Hydrogen atoms and the
anion were omitted for clarity. Thermal ellipsoids are drawn at the 50% probability level. Colour coding: N: blue, Cu: brown, Zn:
magenta.
nacBn2Zn.[3] As in nacnacBn2Zn, the molecule is located on plane of the diketiminate ligand and thus form ladder-like
a crystallographic C2 axis and CH–π interactions between one-dimensional chains of copper and zinc centres (Fig-
CH2 and phenyl groups (2.8 Å) stabilise a regular geometry ure 4). Those are interconnected by the same type of chains
close to S4 symmetry. Given the absence of inter- or intra- formed by the remaining diketiminate ligands, resulting in
molecular hydrogen bonding involving the pyridyl nitrogen, a two-dimensional grid of alternating copper and zinc
this structural similarity is not surprising. Indeed, from the centres. The 2D coordination polymers are stacked along
structural data we cannot exclude that the nitrogen position the crystallographic c-axis in alternation with the [PF6]–
might be disordered between N3 and C8.
anions (Figure 5). Steric constraints introduced by the for-
In the coordination polymer 4 (Figure 3, Table 1), the co- mation of the two-dimensional network exclusively affect
ordination geometry around the Zn atom remains close to the CuPy4 fragment, which displays two N–Cu–N angles
S4 symmetry. Zn–N distances [1.982(2)–1.991(2) Å] are widened to 130° and 135° and a bending of the Cu–N
identical to those in nacnacBn2Zn[3] and 3 (Table 1). The bonds of 7–14° out of the mean planes of the pyridine li-
copper(I) centre has a distorted tetrahedral coordination
geometry with N–Cu–N angles ranging from 97° to 135°.
Cu–N distances (Table 1) are comparable to those in other
[CuPyR4]+ cations (1.99–2.11 Å).[11,12]
Each nacnac2Zn unit is connected to four different cop-
per centres. The pyridyl rings are perpendicular to the mean
Figure 4. Grid-like structure formed by alternating zinc (magenta)
and copper atoms (brown) in the crystallographic a,b-plane. The
two interconnected 1D coordination polymers formed by the diket-
imine ligands are indicated in red and blue, respectively.
Figure 5. Stacking of the 2D Zn–Cu coordination polymers along
the c-axis. Zn: magenta spheres, Cu: brown spheres, F: green, P:
orange. Atoms in red and blue indicate the two interconnected 1D
coordination polymers (see Figure 4).
Eur. J. Inorg. Chem. 2011, 331–335
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333

É. Rousset, T. J. J. Whitehorne, V. Baslon, C. Reber, F. Schaper
FULL PAPER
2-[(3-Pyridylmethyl)amino]-4-[(3-pyridylmethyl)imino]pent-2-ene (1):
A mixture of acetylacetone (5.0 g, 50 mmol) and concentrated hy-
drochloric acid (12 m, 16.6 mL, 0.20 mol) in toluene (50 mL) was
stirred for 10 min, resulting in a pale yellow solution. 3-(Ami-
nomethyl)pyridine (10.8 g, 0.10 mol) was added slowly under agita-
tion (exothermic), the mixture stirred for another 10 min and fi-
nally refluxed with a Dean–Stark apparatus for azeotropic water
removal for 2 d. After cooling to room temperature a brown pre-
cipitate appeared. Toluene was discarded by decantation and the
obtained solid treated with excess aqueous KOH. The aqueous
phase was extracted with toluene until the organic phase remained
colourless. The combined organic phases were dried with Na2SO4
and the solvent evaporated to yield 1 as a brown oil of sufficient
purity for subsequent reactions (12.2 g, 43%). An analytically pure
sample was obtained by recrystallisation from toluene at –30 °C to
gands. The nacnac2Zn fragment, on the other hand, dis-
plays a coordination geometry essentially identical to that
of nacnacBn2Zn[3] and 3, serving as desired as a geometri-
cally inert building block. Use of metalloligands in the con-
struction of metal–organic frameworks is a subject of con-
tinuing interest,[13,14] and the use of N-alkyl-functionalised
diketiminate ligands in the secondary building block 4 pres-
ents a more easily accessible and more readily adaptable
alternative to back-bone-functionalised acetylacetonates
used for this purpose.[15–21]
Luminescence
1
Coordination polymer 4 is luminescent in the solid state
at room temperature with an intense and broad emission
band centred at 670 nm (full width at half maximum =
200 nm). The emission is short-lived and excited-state life-
times are shorter than 30 ns (instrumental limit). Emission
from 4 in the solid state occurs at significantly lower energy
than that reported for [CuPy4]+ cations (525 nm)[22] or for
other coordination polymers based on [CuPyR4]-units
(540 nm).[23] The zinc complex 2, on the other hand, shows
a weak absorption band (λmax = 510 nm) in toluene solu-
tion, the excitation of which leads to a weak emission band
at 550 nm. In the solid state 2 shows emission around
615 nm. We thus assign the emission in 4 to be centred on
the zinc bis(diketiminate) fragment, while the Cu cation acts
only as a structural element.
yield orange crystals. H NMR (CDCl3): δ = 11.36 (s, 1 H, NH),
8.49 (br. s, 4 H, Py C2, C6), 7.47 (d, J = 7.5 Hz, 2 H, Py C4), 7.14
(m, 2 H, Py C5), 4.68 [s, 1 H, HC(C=N)2], 4.44 (s, 4 H, CH2), 1.96
(s, 6 H, Me) ppm. 13C NMR (CDCl3): δ = 161.4 (C=N), 148.8 (Py
C2/C6), 148.0 (Py C2/C6), 135.9 (Py C3/C4), 134.8 (Py C3/C4),
123.3 (Py C5), 95.5 [HC(C=N)2], 48.0 (CH2), 19.6 (Me) ppm.
C17H20N4 (280.37): calcd. C 72.83, H 7.19, N 19.98; found C 72.71,
H 7.57, N 19.76.
2-[(3-Pyridylmethyl)amino]pent-2-en-4-one (acnacCH2PyH): A solu-
tion of acetylacetone (0.5 g, 5 mmol) and 3-(aminomethyl)pyridine
(0.54 g, 5 mmol) in toluene (5 mL) was stirred for 24 h. The yellow
oil formed was isolated by decantation and dried under vacuum
(0.89 g, 94%, Ͼ90% purity according to NMR). An analytically
pure sample was obtained by recrystallisation from toluene at
1
–25 °C. H NMR (CDCl3): δ = 11.02 (s, 1 H, NH), 8.39 (br. s, 2
H, Py C2, C6), 7.47 (d, J = 8 Hz, 1 H, Py C4), 7.15 (m, 1 H, Py
C5), 4.94 [s, 1 H, HC(C=N)(C=O)], 4.34 (d, J = 6 Hz, 2 H, CH2),
1.89 (s, 3 H, Me), 1.79 (s, 3 H, Me) ppm. 13C NMR (CDCl3): δ =
195.3 (C=O), 162.2 (C=N), 148.6 (Py C2/C6), 148.1 (Py C2/C6),
134.0 (Py C3/4), 133.3 (Py C3/4), 123.3 (Py C5), 96.0 (CH), 43.8
(CH2), 28.6 (Me), 18.5 (Me) ppm. C11H14N20 (426.37): calcd. C
69.45, N 14.72, H 7.42; found C 69.07, N 14.88, H 7.42.
Conclusions
Incorporation of pendant donor groups into N-alkyl-
substituted diketiminate complexes afforded geometrically
stable zinc complexes that are suitable for application as
secondary building blocks. Coordination of 2 to four dif-
ferent metal centres in 4 indicates that their chemistry might
be further extended to polynuclear complexes.
nacnacCH2Py2Zn (2): To zinc diethyl (92 μL, 0.9 mmol) in toluene
(0.5 mL) was added a solution of 1 (487 mg, 1.7 mmol) in toluene
(1 mL). Ethane evolution was observed and the solution stirred for
30 min at ambient temperature. Evaporation of toluene afforded 2
as a brown oil (0.51 g, 94%). Purity according to NMR: Ͼ5%.
Recrystallisation by diffusion of hexane into a toluene solution of
2 afforded dark-yellow microcrystals. 1H NMR (C6D6): δ = 8.45
(br. s, 4 H, Py C2), 8.36 (d, J = 4 Hz, 4 H, Py C6), 6.97 (d, J =
7.5 Hz, 4 H, Py C4), 6.59 (m, Py C5), 4.31 [s, 2 H, HC(C=N)2],
3.77 (s, 8 H, CH2), 1.61 (s, 12 H, Me) ppm. 13C NMR (C6D6): δ =
168.1 (C=N), 150.1 (Py C2/6), 148.6 (Py C2/6), 136.4 (Py C3/4),
134.7 (Py C3/4), 123.2 (Py C5), 94.9 [HC(C=N)2], 52.0 (CH2), 22.4
(Me) ppm. C34H38N8Zn (624.11): calcd. C 65.43, N 17.95, H 6.14;
found C 65.43, N 17.56, H 6.61.
Experimental Section
General: All reactions, except ligand synthesis, were carried out un-
der nitrogen using Schlenk or glove-box techniques. Solvents were
dried by passage through activated aluminium oxide (MBraun SPS)
and de-oxygenated by repeated extraction with nitrogen. C6D6 was
distilled from Na and de-oxygenated by three freeze–pump–thaw
cycles. NacnacBnZnEt was prepared according to literature pro-
cedures.[3] All other chemicals were obtained from commercial sup-
pliers and used as received. Elemental analyses were performed by
the Laboratoire d’Analyse Élémentaire (Université de Montréal).
NMR spectra were recorded with a Bruker DRX 400 MHz spec-
trometer and referenced to residual solvent (C6D6, 1H: δ = 7.15,
13C: δ = 128.02. CDCl3, 1H: δ = 7.26, 13C: δ = 77.0 ppm). Emission
spectra in solution were obtained with a Cary Eclipse Fluorescence
spectrometer. The luminescence spectrum of 4 in the solid state
was measured using a Renishaw “inVia” Raman microscope system
equipped with a CCD detector at ambient temperature. The exci-
tation source was the 488 nm line of an Argon ion laser. Samples
were prepared under nujol in the glove box.
(nacnacCH2Py)(nacnacBn)Zn (3): To a solution of nacnacBnZnEt
(0.44 g, 1.2 mmol) in toluene (1 mL) was added a solution of 1
(0.33 g, 1.2 mmol) in toluene (1 mL). The mixture was heated to
60 °C for 1 h. The solvent was evaporated, the resulting yellow oil
was re-dissolved in a minimum of toluene and crystallised at –30 °C
by slow diffusion of hexane into this solution to yield 3 in the form
of orange crystals (40%). 1H NMR (C6D6): δ = 8.53 (s, 2 H, Py
C2), 8.40 (d, J = 4 Hz, 2 H, Py C6), 6.90–7.15 (m, 12 H, Py C4,
Ph), 6.63 (m, 2 H, Py C5), 4.40 (s, 1 H, CH), 4.34 (s, 1 H, CH),
4.04 (s, 4 H, CH2), 3.88 (s, 4 H, CH2), 1.73 (s, 6 H, Me), 1.59 (s, 6
H, Me) ppm. 13C NMR (C6D6): δ = 167.8 (C=N), 167.7 (C=N),
334
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Formation of a 2D Copper–Zinc Coordination Polymer
149.8 (Py C2/6), 148.1 (Py C2/6), 141.5 (ipso Ph), 136.6 (Py C3/4),
134.3 (Py C3/4), 127.4 (Ph), 126.5 (Ph), 122.8 (Py C5), 105.8 (Ph),
Supporting Information (see also the footnote on the first page of
this article): Emission spectrum of 4, absorption and emission spec-
94.4 (CH), 94.3 (CH), 54.1 (CH2Ph), 51.7 (CH2Py), 22.0 (Me), 21.0 trum of 3, details of the X-ray diffraction studies (CIF).
(Me) ppm. C36H40N6Zn (622.11): calcd. C 69.50, N 13.51, H 6.48;
found C 69.25, N 13.08, H 6.58.
Acknowledgments
[(nacnacCH2Py2Zn)Cu]n[PF6]n (4): With care, the following phases
were layered in a Schlenk flask: (i) 2 (0.30 g, 0.4 mmol) in toluene
(2 mL), (ii) toluene (1 mL), (iii) acetonitrile (1 mL), and (iv)
E. R. received a JCEMolChem. stipend from the European Com-
munity. We thank Prof. G. Hanan for allowing to use his spectrom-
[Cu(NCMe)4][PF6] (0.163 g, 0.4 mmol) in acetonitrile (2 mL). After
eters.
36 h yellow crystals formed at the interface. C34H38CuF6N8PZn
(832.60): calcd. C 49.05, H 4.60, N 13.46; found C 48.64, H 3.81,
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RULVUP, SADLIT, XEFKOI, XIQZIH.
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Table 2. Details of X-ray structure studies.
3
4
Formula
C36H40N6Zn
C34H38CuN8Zn·PF6
832.60; 1.552
200; 852
Mw [gmol–1]; dcalcd. [gcm–3] 622.11; 1.304
T [K]; F(000)
Crystal system
Space group
a [Å]
b [Å]
c [Å]
200; 1312
monoclinic
C2/c
14.7946(4)
15.2285(4)
14.0689(4)
90
triclinic
¯
P1
9.4348(2)
9.7075(2)
19.9335(5)
77.795(1)
α [°]
β [°]
90.739(2)
90
3169.45(15); 4
4.2–72.1; 0.99
20757; 0.019
3105; 0.069
1.337
0.056; 0.145
0.056; 0.145;
1.050
87.103(1)
88.567(1)
γ [°]
V [Å3]; Z
1781.94(7); 2
2.2–72.1; 0.96
23586; 0.026
6770; 0.035
2.592
0.037; 0.105
0.042; 0.108; 1.062
θ range [°]; completeness
Collected refl.; Rsigma
Independent refl.; Rint
μ [mm–1]
I Ͼ 2σ(I): R1(F); wR(F2)
All data: R1(F); wR(F2);
GoF(F2)
Residual electron density
0.40, –0.77
0.42, –0.50
[25] G. M. Sheldrick, Bruker AXS Inc., Madison, USA, 1996 and
2004, Bruker Area Detector Absorption Corrections.
[26] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112.
Received: August 24, 2010
CCDC-796290 (for 3) and -796291 (for 4) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Published Online: December 14, 2010
Eur. J. Inorg. Chem. 2011, 331–335
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
335