Job/Unit: I20783
/KAP1
Date: 25-09-12 15:47:01
Pages: 10
C. L. Schmidt, M. Jansen
FULL PAPER
A colourless volatile solid formed on the cold wall of the glass
funnel. This colourless solid was not stable at room temp. After a
short time (Ͻ10 min) the solid turned yellow, thereby restoring the
polyisocyanate. The overall yield of this depolymerisation reaction
was between 30 and 50%.
mode. The samples were prepared by mixing DMSO solutions of
the oligomer and the matrix in the ratio 1:50. The GC–MS data
was recorded with a TSQ 700 (Fa. Finnigan MAT, Bremen).
Theory: Atomic-charge calculations were performed using the
Gaussian program.[26] Calculations have been performed using
DFT with the hybrid functional B3LYP/6-31G(d). The geometrical
parameters used were obtained from recent structural studies.[8]
Single-Crystal X-ray Diffraction: For single-crystal studies, the
crystals were isolated directly from the solution. The collection of
the diffraction intensities was performed with a SMART-APEX
CCD X-ray diffractometer (Bruker AXS Inc.) with graphite-mono-
chromated Mo-Kα radiation. Low-temperature measurements were
carried out with a 700 series cryostream cooler (Oxford Cryosys-
tems). The reflection intensities were integrated with the SAINT
subprogram[22] contained in the SMART software package.[23] An
empirical absorption correction (SADABS)[24] was applied. The
crystal structures were solved by direct methods and refined by
full-matrix least-squares procedures with the SHELXTL software
package.[25]
Supporting Information (see footnote on the first page of this arti-
cle): Crystallographic data and details of the refinement procedures
for the structurally characterised molecular intermediates (Tables
S1–S6). In addition, further experimental data is presented (Figures
S1–S5).
Acknowledgments
The authors would like to thank Paulina Ruff and Jasmin Jarczak
for preparative support, Dr. Jürgen Nuss for collecting the X-ray
diffraction data and Dr. Aswin Verhoeven for collecting solid-state
NMR MAS spectroscopic data. Dr. C. L. Schmidt also thanks the
Fonds der Chemischen Industrie (FCI) as well as the Studienstif-
tung des Deutschen Volkes for scholarships and support.
CCDC-879853 (for 1), -879856 (for 2), -879857 (for 5) and -879858
(for 6) contain the supplementary crystallographic data for this pa-
per. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
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Schnick, Chem. Commun. 2009, 1541–1543.
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[7] a) C. L. Schmidt, PhD Thesis, University of Stuttgart, Ger-
4757/); b) S. J. Makowski, M. Hörmannsdorfer, W. Schnick, Z.
Anorg. Allg. Chem. 2010, 636, 2584–2588.
Further details of the crystal-structure investigations for
3
[C3N3(COO)3K3·2H2O] and 4 [C3N3(COCl)3] can be obtained from
the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leo-
poldshafen, Germany, on quoting the depository numbers CSD-
424611 (for 3) and -424610 (for 4).
X-ray Powder Diffractometry: For the XRD analysis, the samples
were carefully placed between plastic foil and measured in trans-
mission geometry. X-ray diffraction studies have been performed
with a STOE STADI P instrument with a linear PSD detector and
with Mo-Kα1 as well as Cu-Kα1 radiation from a curved Johansson-
type monochromator using Ge(111).
Spectroscopy: Infrared spectroscopy was performed with a FTIR
spectrometer (IFS 113v, Bruker) from 400 to 4000 cm–1 with KBr
as the solid matrix. The substance (1–2 mg) was mixed with KBr
(300 mg) and the powder pressed to pellets (diameter 1 cm, pressed
at 300 MPa).
Energy-Dispersive X-ray Analysis: EDX analysis was performed
with a XL30 TMP (Philips Electron Optics GmbH). An energy-
dispersive detector S-UTW(Li) (EDAX) was used. The powder
sample stored in a glovebox filled with argon was placed on a sam-
ple holder. The sample was attached to the machine with a transfer
chamber to provide inert conditions.
Thermal Analysis: Simultaneous DTA/TG/MS (STA 409, Netzsch)
was performed on a sample placed in a corundum crucible under
flowing argon (100 mLmin–1) at a heating rate of 10 Kmin–1. For
the differential scanning calorimetry (DSC) analysis (DSC 404,
Netzsch), the sample was heated in a corundum crucible with a
heating rate of 10 Kmin–1 under argon; the cooling rate was
2 Kmin–1.
NMR Spectroscopy: Liquid NMR spectra of the dissolved samples
were recorded with a Bruker Avance DPX-300 SB operating at
7.05 T. MAS NMR studies were performed with a Bruker DSX-
400 spectrometer operating at 9.4 T. The sample was filled in a
7 mm ZrO2 rotor. The spinning frequency was 100557 MHz.
Mass Spectroscopy: MALDI-TOF mass spectra were obtained in
reflection mode with a Bruker Daltonics (Bremen) Reflex VI
(337 nm nitrogen laser). The 1,3-dichloro-2,4,6-trinitrobenzene
(DCTB) served as a matrix for analysis of oligomers in the positive
[8] C. L. Schmidt, D. Fischer, H.-J. Himmel, R. Köppe, H.
Schnöckel, M. Jansen, Z. Anorg. Allg. Chem. 2009, 635, 1172–
1178.
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