Supramolecular architectures based on phosphonic acid diesters

Article abstract of DOI:10.1080/10426507.2014.985823

The interest of phosphonic acid dialkyl esters for generation of metal-organic materials is discussed using derivatives of porphyrin and 1,10-phenanthroline series as representative examples.

Full text of DOI:10.1080/10426507.2014.985823

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Phosphorus, Sulfur, and Silicon and the Related
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Supramolecular Architectures Based on Phosphonic
Acid Diesters
a
a
a
a
Alla Lemeune , Alexander Yu. Mitrofanov , Yoann Rousselin , Christine Stern , Roger
a
b
bc
c
Guilard , Yulia Yu. Enakieva , Yulia G. Gorbunova & Sergey E. Nefedov
a
Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR CNRS 6302, 9
avenue A. Savary, 21078 Dijon, France. E-mail:
b
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, Leninskiy p.
3
1-4, Moscow, 119071 Russia. E-mail:
c
N.S. Kurnakov Institute of General and Inorganic Chemistry of RAS, Leninskiy p.31, Moscow,
19991 Russia. E-mail:
Accepted author version posted online: 31 Dec 2014.
1
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To cite this article: Alla Lemeune, Alexander Yu. Mitrofanov, Yoann Rousselin, Christine Stern, Roger Guilard, Yulia Yu.
Enakieva, Yulia G. Gorbunova & Sergey E. Nefedov (2014): Supramolecular Architectures Based on Phosphonic Acid Diesters,
Phosphorus, Sulfur, and Silicon and the Related Elements, DOI: 10.1080/10426507.2014.985823
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SUPRAMOLECULAR ARCHITECTURES
BASED ON PHOSPHONIC ACID DIESTERS
1
1
1
1
Alla Lemeune, * Alexander Yu. Mitrofanov, Yoann Rousselin, Christine Stern, Roger
1
2
2,3
3
Guilard, Yulia Yu. Enakieva, Yulia G. Gorbunova and Sergey E. Nefedov
1
Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR CNRS 6302, 9
avenue A. Savary, 21078 Dijon, France. E-mails: Alla.Lemeune@u-bourgogne.fr;
Roger.Guilard@u-bourgogne.fr
2
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, Leninskiy p. 31-4,
Moscow, 119071 Russia. E-mail: yulia@igic.ras.ru
3
N.S. Kurnakov Institute of General and Inorganic Chemistry of RAS, Leninskiy p.31, Moscow,
1
19991 Russia. E-mail: snef@igic.ras.ru
Abstract The interest of phosphonic acid dialkyl esters for generation of metal-organic
materials is discussed using derivatives of porphyrin and 1,10-phenanthroline series as
representative examples.
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OAlk
OAlk
?
P
O
Mn+
P
O
OAlk
OAlk
n
N
M
N
N
N
or
N
N
M n+ = Zn 2+ , Cu 2+ , Cd 2+
Keywords Phosphonate diester, porphyrin, 1,10-phenanthroline, metal-organic material,
coordination polymer, supramolecular assembly
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INTRODUCTION
Hybrid organic-inorganic materials are drawing a lot of attention due to manifold
attractive properties enabling their use in modern technologies. Ongoing researches are focused
on the development of new scaffolds and design strategies for their assembly. Phosphonate
derivatives have been recognized as convenient molecular precursors for functional materials
starting from late 1970s. Indeed, these organic compounds are simple to prepare according to a
variety of synthetic procedures. Moreover, phosphonic acids and their disilyl esters react with
many metal derivatives under mild conditions providing robust metal−OP bonds which can be
used for generation of coordination polymers including metal-organic frameworks (MOFs), for
synthesis of organic-inorganic hybrid materials based on titania or zirconia as well as for
1
fabrication of thin film materials. To prepare these materials, phosphonic acids are currently
used as key molecular precursors. Surprisingly the supramolecular assembly and grafting of
phosphonate monoalkyl- and dialkyl esters are scarcely studied despite their availability and
stability. This report briefly illustrates the interest of phosphonic acid dialkyl esters for
generation of metal-organic materials (MOMs) using derivatives of porphyrin (M-1a-c, M-2a-e
and M-3a-e) and 1,10-phenanthroline (4a-d and 5a-d) series (Figure 1).
Porphyrinic N- or O-donors are widely used linkers for MOMs and important artificial
2
models for natural supramolecular assemblies playing a key role in the photosynthesis process.
1
,10-Phenanthrolines are widely studied as excellent chelators in traditional coordination
compounds but their use for preparation of coordination polymers are still limited by rare
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examples. Comparative studies of these structurally different series are useful to demonstrate
the general character of our synthetic approach providing new topologies and functionalities to
MOMs.
RESULTS AND DISCUSSION
In this context, we have faced for the need of diethoxyphosphoryl substituted porphyrins
and 1,10-phenanthrolines and developed experimental procedures of their synthesis according to
4
Hirao reaction. Free bases and zinc complexes of bromoporphyrins M-6a-e, M-7a-e react with
diethyl phosphite in the presence of Pd(OAc) /PPh catalytic system and triethylamine. Choice
2
3
of the reaction solvent is crucial for the product yield. meso-(Diethoxyphosphoryl)porphyrins M-
2
a-e, M-3a-e were obtained in good yields only when the reactions were performed in ethanol at
5
reflux (Scheme 1).
In contrast, -bromoporphyrin M-8 does not react with diethyl phosphite under these
conditions owing to its low solubility in this solvent. Fortunately, the reaction smoothly proceeds
6
in toluene at reflux (Scheme 2). For both porphyrin series, higher yields of the target products
were obtained using a large excess of diethyl phosphite and base (up to 50 equivalents) and a
high catalyst loading (up to 0.5 – 1 equivalent).
Being strong chelators, 1,10-phenanthroline halides competed with triphenylphosphine to
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coordinate the palladium centre, rending the catalytic reaction impractical. The target products
were obtained in good yields in toluene or dioxane at reflux when PPh was replaced by
3
7
bidentate 1,1’-bis(diphenylphosphino)ferrocene (dppf) (Scheme 3).
Investigation on the supramolecular organization of the newly synthesized phosphonic acid
diesters was started using zinc porphyrinates Zn-1a,b, Zn-2a-e and Zn-3a-e, which are
structurally programmed for self-assembly. Indeed, both - and meso- derivatives generate
supramolecular assemblies due to the connection of the molecules via weak M…O=P
5
,6
coordination bonds (Figure 2). According to systematic studies of meso-porphyrinates Zn-2a-e
and Zn-3a-e, it appears that the solid state supramolecular organization is determined by the
number and position of phosphonate groups as well as the nature of the aryl substituents at the
macrocycle periphery.
Varying only the substituent at the para-position of the benzene ring, tetrameric or infinite 1D
structures were obtained for Zn-2a-e. According to NMR studies, these architectures also exist
in toluene-d8 and chlorinated solvents at low temperatures. Additional dimensionality of the
polymers can be encoded via the introduction of the second phosphonate group at the
5
,8
tetrapyrrolic macrocycle. For example, M-3a (M = Zn, Cu, Cd) and Zn-3e generate 2D
networks in the solid state and in solution.
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Thus, the complexes of diethoxyphosphoryl substituted porphyrin generate stable self-
assemblies which are excellent models for natural porphyrinic systems and allow to get insight
into the influence of structural parameters of molecular precursors on the self-assembly process.
Showing the possibility to generate supramolecular assemblies using M…O=P
coordination bonds, our interest was also to develop a general approach to coordination polymers
based on phosphonate diesters using external metal connectors. Binuclear paddle-wheel (PW)
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complexes M (-O CR) L
2
are a priori appropriate assembling nodes. Mixing M (-O C-t-
2
2
4
2
2
Bu) (NCMe)
2
and M-3a (M=Cu, Ni, Pd), homo- and heterometallic infinite architectures M-11
4
were prepared and characterized by single crystal X-ray diffraction analysis (Scheme 4).
When phenanthroline 5a was reacted with Cu
product Cu (µ-OOCMe) (µ-O,O’-5a) (12) was obtained. This compound exhibits an
unusual polymeric structure in the crystals. Indeed bimetallic PW fragments Cu (µ-
OOCMe) are linked in axial positions to the disubstituted phenanthroline ligand 5a
2
(µ-OOCMe)
4
(THF)
2
, a crystalline
2
4
2
4
coordinated to the metal atoms only by the two oxygen donor atoms of the phosphonate
groups (Figure 3, left panel).
Evidently, to construct infinite architectures, various external metal nodes may
replace PW linking moieties. Thus an interesting example was obtained reacting
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
2
phenanthroline 4b with Cu(NO
3
)
2
H O in a 1:1 ratio. 1D polymeric structure of the
complex 13 results from the coordination of Cu(II) centers to the oxygen atoms of the
phosphoryl groups of the neighbouring phenanthroline ligands (Figure 3, right panel).
CONCLUSIONS
Reported data show the propensity of the phosphonic acid diesters for the engineering of
supramolecular coordination complexes and infinite frameworks by either direct interaction of
molecular precursors or through their connection using external metal nodes.
Acknowledgements This work was carried out in the frame of the International Associated
French–Russian laboratory LAMREM supported by the CNRS, the RAS and RFBR (grants 12-
0
3-93110, 12-03-93114).
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Figure 1 Structures of the studied diesters of phosphonic acids.
Figure 2 Schematic representation of supramolecular assemblies Zn-1, Zn-2 and M-3
determined by single crystal X-ray analysis.
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Figure 3 Structure of 1D polymers based on (diethoxyphosphoryl)phenanthrolines 5a
(left panel) and 4b (right panel) determined by single crystal X-ray diffraction analysis.
Scheme 1
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Scheme 2
Scheme 3
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Scheme 4
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