Synthesis and Structure of an Arylmanganese(II)

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SHORT COMMUNICATION
DOI: 10.1002/zaac.201400302
Synthesis and Structure of an Arylmanganese(II) 8-Hydroxyquinolinate
Tetranuclear Cluster
Iwona Justyniak,*[a] Arkadiusz Kornowicz,[b] Daniel Prochowicz,[b] Kamil Sokołowski,[a]
and Janusz Lewiński[a,b]
Keywords: 8-Hydroxyquinoline; Manganese; Cluster compounds; Self-assembly
Abstract. Reaction of 8-hydroxyquinoline with dimesitylmanganese
[(Mes)2Mn]3 results in the formation of arylomanganese(II) tetranuclear cluster [(Mes)2Mn4(q)6]·4PhMe (1) supported by the quinolinate
ligands. Molecular studies showed that the centrosymmetric molecule
of 1 contains two pairs of manganese atoms of different coordination
modes formed by association of the two dinuclear [MesMn(q)][Mn(q)2]
moieties. A detailed analysis of the crystal structure of 1 revealed that
single molecules of 1 self-assemble through a network of intermolecular CHar···π interactions into closely packed quasi-grid 2D layers.
Introduction
nescent alkylzinc 8-hydroxyquinolate complexes was reported.[7d,7e] In continuing the development of efficient synthetic
methods of ZnII[7d–7f,8] and MnII[9] compounds as starting materials for further transformations, herein the synthesis, structural characterization, and luminescence properties of the first
arylmanganese(II) 8-hydroxyquinolinate cluster is reported.
The organometallic chemistry of manganese(II) has attracted
major interest due to a significant ionic contribution to the
manganese(II)–carbon bonds in comparison to those of other
first row metals.[1] This lower covalency resulted in a range
of novel applications in organic synthesis and polymerization
catalysis.[2] The organometallic complexes of manganese that
have attracted the most attention in recent years are the homoleptic alkyl and aryl derivatives.[3] The series of organomanganese(II) complexes, such as Mn(CH2tBu)2,[3a]
Mn{C(SiMe3)3}2,[3b] {Mn(CH2CMe2Ph)2}2,[3c] Mn3(Mes)6
(Mes = C6H2–2,4,6-Me3),[3d] MnMes*2 (Mes* = C6H3–2,6Mes2),[3e] MnAr2 (Ar = C6H3–2,6-Mes2)[3f] have been reported
and structurally characterized. Among them, Mn3(mes)6 has
proved to be a valuable starting material for the preparation of
a number of other novel MnII complexes.[4] For instance, Floriani and co-workers reported a series of unusual MnII aryl species from its reaction with triphenylborane and pyrrole-based
ligands.[4a,4b] More recently, Wright and co-workers reported
on the reactions of manganocene, Cp2Mn (Cp = C5H5), with
N,N⬘-bifunctional ligands, including 8-aminoquinoline.[5]
The chemistry of metal quinolinates has attracted a vast
amount of attention due to their applications especially in the
modern electronics as material to produce organic light-emitting diodes.[6] However, the organometallic chemistry of complexes with quinolinate ligands is relatively poorly explored.[5,7] For example, only recently, a new family of lumi* Dr. I. Justyniak
E-Mail: [email protected]
[a] Institute of Physical Chemistry
Polish Academy of Sciences
44/52 Kasprzaka
Warsaw 01-224, Poland
[b] Warsaw University of Technology - Chemistry
Noakowskiego 3
Warsaw 00-664, Poland
Z. Anorg. Allg. Chem. 0000, 䊏,(䊏), 0–0
Results and Discussion
The reaction of (Mes)6Mn3[10] with 1 equiv. of 8-hydroxyquinoline (q-H) resulted in the formation of a organomanganese compound supported by the quinolinate ligands with
the formula [(Mes)2Mn4(q)6] (1), irrespective of the molar ratio of the reactants used (Scheme 1). Complex 1 was characterized by elemental analysis and its structure was determined
by single-crystal X-ray diffraction. Suitable crystals of 1, in
the form of a toluene solvate 1·4PhMe, for X-ray structure
determination were obtained at low temperature after crystallization from THF/toluene mixture. The dark red crystals of
1·4PhMe were air-sensitive and changed into black in 10 min
when exposed to air.
Scheme 1. Synthesis of complex 1.
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I. Justyniak et al.
SHORT COMMUNICATION
The basic skeletal arrangement of 1 can be described as an
inversion-related, corner-removed, face-shared cubane, which
is a common structural type in mixed-valence MnII2MnIII2
clusters,[11] and to the best of our knowledge, compound 1 is
the first example of an arylmanganese(II) cluster exhibiting
this type of motif. The symmetric [MesMn(q)][Mn(q)2] unit
consists of one five-coordinate and one six-coordinate manganese(II) atom. The coordination sphere of the five-coordinate
MnII atom is completed by one terminally bound mesityl
group, one chelated quinolin-8-olate anion, and the two μ2-O
atoms of two other quinolin-8-olate anions, which themselves
engage in chelation to the other MnII atoms. The arrangement
of the Mn(1) atom is best described as a highly distorted trigonal bipyramid. The equatorial plane, defined by the two μ2-O
atoms [i.e. O(1), O(3⬘)] and one nitrogen atom N(2), is planar
with bond angles around the manganese atom in the range of
96.6(8)–130.0(7)°. The axial positions are occupied by the aryl
carbon C(1) atom and the μ3-O(2) atom with an O(2)–Mn(1)–
C(1) angle of 163.7(1)°. The Mn(1)–C(1) bond length is
2.191(1) Å, which is similar to the length of the analogous
bond in other arylmanganese(II) compounds.[3e,3f,4e] The
Mn(2) atom is six-coordinate as it is linked to two μ3-O atoms
of the anions that chelate the mesityl-bound metal atom, and
is chelated by two quinolin-8-olate ligands. This metal atom
adopts a distorted octahedral coordination environment with
essentially equal Mn–O and Mn–N bond lengths (average:
2.190 Å).
Interestingly, a more detailed analysis of the supramolecular
structure of 1·4PhMe shows that single molecules of 1 utilize
their shape to form 1D noncovalently-bonded chains, in which
adjacent molecules of 1 are connected by a network of intermolecular complementary CHar···π interactions mediated by
toluene molecules (with the distances in the range of 2.781–
2.92 Å, dotted lines in Figure 1b). The polymer chains are further organized through a subsequent self-assembly process induced by C–Har···π interactions into close-packed of quasi-grid
2D layers (Figure 1c).
To determine the spectroscopic properties of 1, UV/Vis
spectroscopic and photoluminescence measurements were carried out and the corresponding absorption and emission spectra
are shown in Figure 2. The absorption and emission bands of
1 in THF have maxima at 380 nm and 580 nm, respectively
and are similar to the reported data of other MnII complexes
with quinolinate ligands.[12]
Figure 1. (a) Molecular structure of 1; hydrogen atoms are omitted for
clarity. Selected bonds lengths /Å and angles /°: Mn1–O1, 2.164(2);
Mn1–O2, 2.359(2); Mn1–O3’, 2.107(2); Mn1–N2, 2.280(3); Mn1–C1,
2.192(3); Mn2–O1, 2.156(2); O1–Mn1–O2, 73.72(8); O1–Mn1–O3’,
96.68(9), O1–Mn1–N2, 130.06(10), O2–Mn1–N2, 70.51(9), O2–Mn1–
O3’, 76.82(9). (b) View of the supramolecular arrangement in a 1D
coordination polymer of 1 along the b axis (the dotted lines represent
C–Har···π cooperative interactions). (c) View of the extended 2D network in the crystal structure of 1 with entrapped toluene molecules.
Conclusions
The arylmanganese(II) 8-hydroxy-quinolinate complex
[(Mes)2Mn4(q)6]·4PhMe (1) exhibiting luminescence properties was synthesized and characterized. Compound 1 is a very
rare example of a heteroleptic organomanganese(II) complex,
and can also be potentially used as convenient precursor for
further structural modifications by M–C bond functionalization. It is attempted to use these type precursors to design
novel homo- and heterometallic entities with desired properties.
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Figure 2. Absorbance and photoluminescence spectra of 1 in THF;
excitation at 380 nm.
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Arylmanganese(II) 8-Hydroxyquinolinate Tetranuclear Cluster
Experimental Section
References
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(Elementar Analysensysteme GmbH). The absorption measurement
was carried out with a Shimadzu UV3100 spectrophotometer. The luminescence spectrum was recorded with a Hitachi F-7000 spectrophotometer.
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Synthesis of [(Mes)2Mn4(q)6]·4PhMe (1): A solution of 8-hydroxyquinoline (145.16 mg, 1.00 mmol, 145,16 g·mol–1) in toluene (10 mL)
was cooled to –78 °C, and Mn(Mes)2 (4.0 mL of a 0.25 m solution in
THF, 1.00 mmol) was added dropwise. Afterwards, the reaction mixture was warmed to room temperature and stirred for 4 h. Concentration of the obtained solution to the volume of 2 mL and subsequent
crystallization at –25 °C for one week gave small red crystals of 1
(185.6 mg, 44 %). C100H86Mn4N6O6 (1687.54 g·mol–1): calcd.
C 71.18, H 5.14 %; found: C 72.16, H 5.09 %.
X-ray Crystallography: The data were collected at 100(2) K with a
Nonius Kappa CCD diffractometer[13] using graphite monochromated
Mo-Kα radiation (λ = 0.71073 Ĺ). The crystal was mounted in a nylon
loop in a drop of silicon oil to prevent the possibility of decay of the
crystal during data collection. The unit cell parameters were determined from ten frames and refined on all data. The data were processed with DENZO and SCALEPACK (HKL2000 package).[14] The
structure was solved by direct methods using the SHELXS97 program
and was refined by full-matrix least-squares on F2 using the program
SHELXL97.[15] All non-hydrogen atoms were refined with anisotropic
displacement parameters. The hydrogen atoms were refined isotropically on calculated positions using a riding model with their Uiso
values constrained to 1.5 Ueq of their pivot atoms for terminal sp3
carbon atoms and 1.2 times for all other carbon atoms.
Crystal Data for 1: C100H86Mn4N6O6: M = 1687.51, crystal dimensions 0.38 ⫻ 0.28 ⫻ 0.14 mm3, triclinic, space group P1̄ (no. 2), a =
12.6440(5) Å, b = 13.4550(5) Å c = 14.3050(5) Å, α = 68.124(2) °, β
= 83.485(2) °, γ = 67.201(2) °, U = 2080.59(13) Å3, Z = 1, F(000) =
876, Dc = 1.347 g·cm–3, T = 100(2) K, μ(Mo-Kα) = 0.653 mm–1, Nonius Kappa-CCD diffractometer, θmax = 24.71°, 6849 unique reflections.
Refinement converged at R1 = 0.0697, wR2 = 0.1247 for all data and
528 parameters [R1 = 0.0542, wR2 = 0.1178 for 5710 reflections with
Io ⬎ 2σ(Io)]. The goodness-of-fit on F2 was equal 1.071. A weighting
scheme w = [σ2(Fo2 + (0.0418P)2 + 3.1964P]–1 where P = (Fo2 +
2Fc2)/3 was used in the final stage of refinement. The residual electron
density = +0.66 /– 0.37 e·Å–3.
Crystallographic data (excluding structure factors) for the structure 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 number CCDC-1002239 (Fax: +44-1223-336-033; E-Mail:
[email protected], http://www.ccdc.cam.ac.uk).
Acknowledgements
The authors would like to acknowledge the project operated within the
National Science Centre (DEC-2011/01/B/ST5/06338) (I.J.) and the
European Union funds by the European Social Fund (A.K., K.S.) for
financial support.
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SHORT COMMUNICATION
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[13] Kappa CCD Software, Nonius B. V., Delft, The Netherlands,
1998.
[14] Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307–
326.
[15] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Received: June 27, 2014
Published Online: 䊏
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Arylmanganese(II) 8-Hydroxyquinolinate Tetranuclear Cluster
I. Justyniak,* A. Kornowicz, D. Prochowicz, K. Sokołowski,
J. Lewiński ......................................................................... 1–5
Synthesis and Structure of an Arylmanganese(II) 8-Hydroxyquinolinate Tetranuclear Cluster
Z. Anorg. Allg. Chem. 0000, 0–0
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