XIV
h
International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
323
T8: P–2
The role of secondary bonding and solvent effect on supramolecular
assembly of mercury coordination compounds
Maciej Kubicki
1
, Ghodrat Mahmoudi
2
, and Elena López-Torres
3
1
Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89b,61-614 Poznan,
Poland, e-mail: mkubicki@amu.edu.pl
2
Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box55181-83111,
Maragheh, Iran.
3
Departamento de Química Inorgánica, Facultad de Ciencias, Módulo 07, Universidad Autónoma de
Madrid, Ctra. de Colmenar Viejo, Km 15, 28049 Madrid, Spain
Due to their versatile structural diversity and potential applications in different areas from
catalysis to nonlinear optics self-assembled metal complexes have attracted considerable
attention in crystal engineering and supramolecular chemistry, controlling the architecture of
self-assembled species influenced by the structure of ligands, coordination geometry of metal
ions, counter-anions, and supramolecular interactions of the coordination compound with its
surroundings. The spherical d
10
configuration of Hg(II) is associated with a flexible coordination
environment, thus the geometries of these complexes can vary from linear to octahedral or even
distorted hexagonal bipyramidal, and severe distortions from ideal coordination polyhedra occur
easily. Furthermore, due to the lability of d
10
metal complexes, the formation of coordination
bonds is reversible, which enables metal ions and ligands to rearrange during the supramolecular
assembly to allow the formation of the thermodynamically most stable structure, by varying the
coordination polyhedron and coordination number of the mercury atom. Consequently,
mercury(II) can readily accommodate different kinds of coordination frameworks, using a
variety of organic ligands along with different inorganic-organic bridging units.
In order to further explore the structural chemistry of mercury(II) compounds with N-donor
ligands, we undertook the systematic synthesis and structural characterization of Hg(II)
complexes of a series of unsymmetrical Schiff base ligands. The goal of this study is to analyze
the competition between anion and ligand HL (Fig. 1) for the coordination sites at the
mercury(II) centre and to probe how the nature of the anion affects the crystal packing. Herein,
we report the self-assembly and resulting structures of nine mercury(II) complexes containing
three different Schiff base ligands (1–9). They have been characterized by different
physicochemical measurements including single-crystal X-ray crystallography. The structural
descriptions have been corroborated with calculations of Hirshfeld surfaces which reveal a
strong effect of non-covalent interactions on the properties of the surfaces. Special attention has
been given to dnorm-and shape index-mapped surfaces, as well as on 2D fingerprints.
Fig. 1. Perspective view of one of the similar mononuclear Hg-complexes.
Keywords: Hg-complexes; interatomic interactions; Hirshfeld surface
XIV
h
International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
324
T8: P–3
The pattern of ν(C=O) VCD bands of isoindolinones in solid phase
Joanna E. Rode
1
, Krzysztof Łyczko
1
, Magdalena Jawiczuk
2
, Robert Kawęcki
3
,
Wojciech Stańczyk
3
, Agnieszka Jaglińska
3
, and Jan Cz. Dobrowolski
1
1
Institute of Nuclear Chemistry and Technology, 16 Dorodna Street, 03-195 Warsaw, Poland,
e-mail: j.rode@ichtj.waw.pl
2
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw,
Poland
3
Siedlce University, 3 Maja Street No 54, 80-110 Siedlce, Poland
The Vibrational Circular Dichroism (VCD) chiroptical spectroscopy has been developed
since early 1970s. However, in the last decade VCD became mature enough for routine chirality
monitoring and control. Still, the method is only rarely used for investigations of substances in
the solid state. In this study, the VCD and IR spectra of four new chiral isoindolinones in the
KBr pellets placed in a rotating holder of the FVS-6000 spectrometer (JASCO, Co., Japan) were
registered in the 1800–1500 cm
–1
range (Fig. 1).
(a)
(b)
(c)
Fig. 1. (a) The R enantiomers of studied (R=Me, nBu, Ph, CH2Ph) isoindolinones;
(b) the IR and VCD spectra of studied molecules; (c) the (R)-Me H-bonds in solid state measured by X-ray.
Presence of two or more bands in the 1800–1500 cm
–1
range of the IR and VCD spectra (Fig.
1b) of isoindolones containing only one C=O moiety, indicates presence of intermolecular
interactions between the molecules in the solid state. The X-ray measurements demonstrated
that the expected C=O∙∙∙H-N interactions in different derivatives form different motifs. To
interpret the IR and VCD spectra of isoindolones in the solid states, the B3LYP-D3/TZVP/PCM
calculations were performed for various structural arrangements found in different unit cells.
The DFT calculations allowed for satisfactory reproduction of the experimental spectra.
Acknowledgment
This work was supported by the National Science Centre in Poland Grant 2013/09/B/ST5/03664. The
Świerk Computing Centre and PL-Grid infrastructure are acknowledged for generous allotment of
computing time.
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