XIV
h
International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
299
T6: P–7
IR and UV study of reversible water-induced structural
transformations of poly(manganese 1,1’-ferrocenediyl-bis(H-
phosphinate)) and poly(cobalt 1,1’-ferrocenediyl-bis(H-phosphinate))
Tatiana Gerasimova
1
, Ruslan Shekurov
1
, Leysan Gilmanova
1
, Sergey Katsyuba
1
,
Valeriy Kovalenko
1
, Vasiliy Milyukov
1
, and Oleg Sinyashin
1
1
Laboratory of physical-chemical analysis, A.E. Arbuzov Institute of Organic and Physical
Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str. 8, Kazan, 420088,
Russian Federation, e-mail: tatyanagr@gmail.com
Flexible or dynamic metal-organic frameworks (MOFs) of the third generation according to
S. Kitagawa classification also called soft porous crystals can undergo reversible structural
transformations upon adsorption/desorption of guest molecules. The fascinating flexibility
phenomena in MOFs offer a wide range of application opportunities emerging when structural
transformations upon adsorption/desorption are accompanied by the simultaneous changes of
physical properties: the color of the MOFs, adsorption selectivity, proton conductivity,
luminescence and magnetic properties. The transformations may be accompanied by the
cleavage and formation of coordination bonds, by the change of the framework dimensionality,
by the change of the metal coordination polyhedra, the slippage of the layers, mechanical
shrinkage of crystals, etc. In these processes the crystallinity is often retained, but in some cases
the crystalline – to – amorphous – to crystalline transformations take place.
Fig. 1. [M(H
2
O)
2
(Fc(PHOO)
2
)·2H
2
O]
n
.
Flexible and hydrolytically stable metal-organic frameworks [M(H
2
O)
2
(Fc(PHOO)
2
)·2H
2
O]
n
,
where M = Mn, Co, have been synthesized using ferrocene-based ligand bearing phosphinic
groups (Fc(PHOOH)
2
= 1,1’-ferrocenediyl-bis(H-phosphinic acid)), Fig. 1. Heating of the MOFs
leads to the elimination of water molecules forming new compounds, which are non porous for
nitrogen, but can selectively adsorb water over methanol and other solvents at 298 K. The
structures of the dehydrated compounds were studied by IR, Raman and UV spectroscopies. It
was shown that both Mn and Co complexes undergo the same changes, analysis of UV spectra
suggest the tetrahedral environment of metal ions in dehydrated form.
Keywords: metal-organic frameworks; ferrocenylphosphinic acids; UV and vibrational spectroscopy;
crystal-to-amorphous transformation
Acknowledgment
This work was supported by the RFBR grant 16-33-00463_mol_a.
XIV
h
International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
300
T6: P–8
Chloro- and bromolactones with p-fluorophenyl group. Synthesis and
spectroscopic properties
Angelika Kamizela
1
, and Barbara Gawdzik
1
1
Institute of Chemistry, Jan Kochanowski University in Kielce, Świętokrzyska st. 15 G, 25-406 Kielce,
Poland, e-mail: angelikakamizela@o2.pl
Halolactones are a group of compounds endowed with a wide range of biological and
sensory properties, which can be used in medicine or the food industry [1]. Chemical
compounds having a lactone moiety have antimicrobial, antiviral, antineoplastic, anti-fungal,
anti-malarial properties [2]. For this reason, many research teams are currently developing new
methods of lactone synthesis or modification of existing ones.
In this paper we present a four-stage pathway for the synthesis of chloro- and bromolactones
with the p-fluorophenyl group and the spectroscopic properties of all the obtained compounds.
The first step was the Grignard reaction of p-fluorophenylmagnesium bromide with 3-
methylcrotonaldehyde. In the second stage of synthesis, unsaturated alcohol was subjected to
Claisen rearrangement. The resulting ester was converted to carboxylic acid by hydrolysis of
KOH in ethanol. The fourth step in the lactones synthesis was the bromo- and chlorotonization
carried out in the presence of NBS and NCS.
The structures of all obtained compounds have been confirmed by IR and NMR spectral
spectroscopy. In addition, X-ray analysis was performed for crystalline lactones.
Keywords: lactone; halolactone; cyclic esters
References
[1] B.
Gawdzik, A. Kamizela, A. Szyszkowska, Chemik 69 (2015) 342.
[2] K. Libiszewska, Biotechnol Food Sci. 75 (2011) 45.
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