Dihydrogen phosphate-containing dinuclear double assemblies that demonstrate phosphate reactivity to the tetrafluoroborate anion

Article abstract of DOI:10.1039/c8cc04900a

The ligands L¹ and L² both form dinuclear assemblies with Cu(ii) and these react with dihydrogen phosphate so that the anion is incorporated within the assembly (e.g. [Cu₂L₂(H₂PO₄)]³⁺). However, in the presence of tetrafluoroborate anions the phosphate undergoes reaction with the anion forming [Cu₃(L¹)₃(O₃POBF₃)]³⁺ and [Cu₂(L²)₂(O₂P(OBF₃)₂)]⁺.

Full text of DOI:10.1039/c8cc04900a

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Dihydrogen Phosphate-containing Dinuclear Double Assemblies
that Demonstrate Phosphate Reactivity to the Tetrafluoroborate
Anion.
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Robert A. Faulkner, Nathan J. Patmore, Craig R. Rice* and Christopher Slater.
www.rsc.org/
1
2
The ligands L and L both form dinuclear assemblies with Cu(II) spacer forms dinuclear double helicates with Cu(II) and
and these react with dihydrogen phosphate so that the anion is contained within this species is a cavity which binds
3
+
incorporated within the assembly (e.g. [Cu
2 2 2 4
L (H PO )] ). However, perchlorate and tetrafluoroborate anions. Reaction of this
in the presence of tetrafluoroborate anions the phosphate with dihydrogen phosphate changes the dinuclear structure to
1
3+
)]
undergoes reaction with the anion forming [Cu
3
(L )
3
(O
3
POBF
3
a trinuclear circular helicate that forms phosphate-phosphate
5i
hydrogen bonded dimers in the solid state.
2
+
and [Cu
2
(L )
2
(O
2
P(OBF
3
)
2
)] .
In this work we show how two ligands that contain two
bidentate pyridyl-thiazole domains, separated by either a 1,2-
Metallo-supramolecular chemistry is the self-assembly of
structurally complex architectures from the coordination of
1
2
diaminoethyl (
dinuclear assemblies upon coordination with Cu(trif)
Cu ](trif) ) and upon reaction with H PO ˉ the dihydrogen
phosphate anion is incorporated within the assembly.
L
) or 1,4-diaminobutyl (
L
) spacer, form
1
suitably instructed ligand strands and metal ions. In the
2
(e.g.
helicate form a ligand is employed that can partition into two
donor domains, each of which coordinates a different metal
[
2
L
2
4
2
4
1
2
ion and a further ligand coordinates the remaining metal sites
n+ 2
However, reaction of
in the reaction of dihydrogen phosphate with the
tetrafluoroborate anion forming a {(POBF )ˉ} moiety. In the
4 2 2 4
L or L with Cu(BF ) and H PO ˉ results
on the cation giving a dinuclear double helicate [M L ] .
2
2
Whilst the linear helicate is arguably the simplest form of
assembly there are many different species that can be formed
3
such as circular helicates, grids, ladders and cages. One
3
2
2+
case of [Cu2(
L
) (H PO )] this reacts with two BF ˉ anions
2
+
) (O P(OBF ) )] whereas [Cu2(
2
4
4
2
1
3+
forming [Cu2(
L
L
) (H PO )]
4
2
2
3 2
2
2
application of metallo-supramolecular chemistry is the self-
assembly of anion receptors. Anions are chemically important
species and their detection and sequestering is an important
area of study. Whilst there has been a great deal of effort in
this area, many anion receptors are often complex to prepare
only reacts once and forms a trinuclear circular helicate
1
3+
) (O P(OBF ))] .
[Cu3(
L
3
3
3
H
N
S
N
N
N
H
N
4
and often require multi-step synthesis. One method to
N
S
circumvent complex synthetic procedures is to generate anion
receptors from self-assembly, where the receptor is not
synthesized in the conventional sense but is rather assembled
in solution, generating a complex architecture from smaller
L1
S
N
H
N
N
N
H
N
5
S
N
pre-programmed chemical fragments. As a result the self-
assembly of metallo-supramolecular species can produce
suitably functionalised architectures that bind anions, forming
receptors that are capable of sensing and sequestering these
important chemical species. For example, we have shown that
L2
1
L and L .
2
Scheme 1. Bis-bidentate ligands
1
L was prepared by reaction of ethylenediamine
a bis-bidentate ligand containing a 1,3-diaminophenylene The ligand
with benzoyl isothiocyanate to give the dibenzoylated
dithiourea derivative. Hydrolysis of this with NaOH gave the
bis-thiourea and reaction with α-bromoacetylpyridine gave the
1
L
2
ligand
. Ligand
L
was made in a similar fashion using 1,4-
diaminobutane.
1
Reaction of
L
with Cu(trif) in MeNO gives a tan-coloured
2
2
solution and analysis by ESI-MS gave an ion at m/z 1335
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1
1
+
} as well as an ion at m/z 593 showed that, unlike the dinuclear assembly formed with
2+
corresponding to {[Cu
corresponding to {[Cu
2
2
(
L
)
2
](trif)
3
(
L
)
2
](trif)
2
}
indicating the formation of Cu(trif)
2
, with the BF
4
6+
ˉ counter anion a trinuclear structure is
1
a dinuclear assembly. Exposure of the solution to diethyl ether formed e.g. [Cu
gave a crystalline material which was analysed by X-ray
crystallography. In the solid-state the ligand partitions into two
separate bidentate binding domains each of which coordinates
a different Cu(II) ion and both of these ions are coordinated by
two bidentate pyridyl-thiazole domains one from each ligand
3 3
(L ) ] .
(Fig. 1). The metal ions coordination sphere is supplemented
by coordination by a triflate counter anion which itself forms a
series of hydrogen bonding interactions to two -NH atoms on
the same ligand strand (Cu-N range 1.948(2) – 2.126(2) Å, Cu-O
2
.1693(19) Å). There is no twist about the ligand strand giving
1
rise to a dinuclear double mesocate.
2 2 2 4 3
Figure 2. Two views of the X-ray structure of [Cu (L ) (H PO )](trif) . Thermal
ellipsoids shown at the 30% probability level. Remaining triflate anions are
omitted for clarity. Colour code: orange, Cu(II); red, O; blue, N; yellow, S; lime F;
grey, C; light orange, P.
In the solid-state the assembly contains three metal ions and
three ligands with each metal ion coordinated by two
bidentate thiazole-pyridyl domains (Cu-N range 1.956(5) -
2.504(5) Å) from two different ligands (Fig 3a – 3c). The
phosphate anion sits in the core of the assembly and
1
Figure 1. Two views of the X-ray structure of [Cu
2
(
L
)
2
](trif) . The complex has coordinates all three Cu(II) ions via three Cu···O coordination
4
crystallographically-imposed inversion symmetry .Thermal ellipsoids shown at bonds (Cu-O range 1.905(4) - 2.013(4) Å) and this is
the 30% probability level. Remaining anions are omitted for clarity. Colour code: supplemented by a multitude of -NH···anion interactions (Fig
orange, Cu(II); red, O; blue, N; yellow, S; lime F; grey, C
.
3d). The most unusual feature of the assembly is one of the
phosphate oxygen atoms is bonded to a -BF3 unit, which
1
Reaction of the mesocate assembly [Cu2(
L
) ](trif) in MeNO
2 4
presumably arises from reaction with the BF ˉ counter anion.
4
2
with half an equivalent of Bu NH PO results in a lime-green The species is also present in the ESI-MS which gave an ion at
4
2
4
1
+
) (O POBF )](BF ) } .
coloured solution from which a crystalline material was m/z 1668 corresponding to {[Cu3(
L
3
3
3
4 2
deposited upon slow diffusion of diisopropyl ether. In the solid
state the dinuclear structure persists and each of the Cu(II)
b
a
ions are again coordinated by two bidentate pyridyl-thiazole
domains from the two different ligands (Fig 2). However, in
this structure a dihydrogen phosphate anion is incorporated
within the assembly which bridges the two Cu(II) ions via
1
3+
coordination of the oxygen atoms e.g. [Cu2(L ) (H PO )] (Cu-N
2 2 4
range 1.974(3) - 2.231(3) Å, Cu-O 1.976(3) and 1.996(3) Å). The
H2PO4 anion is also held within the ligand strand via -
NH···anion interactions with the phosphate oxygen atoms
interacting with a single amine hydrogen atom on each strand.
The remaining amine hydrogen atom forms intermolecular
hydrogen bonding interactions with the triflate counter anions.
d
c
There are a total of three triflate anions present within the
1
anion structure (i.e. [Cu
2
(L
)
2
(H
2
PO
4
)](trif)
3
) indicating that
dihydrogen phosphate is present and has not undergone
further deprotonation. This is further supported by the
2 2
hydrogen bonding interaction between both the O P(OH)
1
L
Figure 3. X-ray structure of [Cu
3
(
)
(O POBF
3 3
3
)](BF
3
)
3
a)
-
d) showing the
units and an anion. The dinuclear structure persists in the gas
3
+
trinuclear assembly and d) partial view of the {Cu
3
(O
3 3
P-OBF )} core and the
phase with ESI-MS analysis giving ions at m/z 1282 and 492
1
+
hydrogen bonding to –NH atoms. Thermal ellipsoids shown at the 30%
probability level. Remaining tetrafluoroborate anions are omitted for clarity.
Colour code: orange, Cu(II); red, O; blue, N; yellow, S; lime F; grey, C; light
orange, P; pink, B (apart from 3b and 3c where the ligand strands have been
coloured for clarity).
corresponding
1
to
{[Cu
2
(
L
)
2
(H
2
PO
4
)](trif)
2
}
and
2+
2 2 4
(L ) (HPO )]} .
{
[Cu
1
Reaction of Cu(BF
4
)
2
·6H
2
O with
L
and half an equivalent of
2
also gives a lime-green
dihydrogen phosphate in MeNO
solution from which crystals are deposited from slow diffusion
of diisopropyl ether. However, analysis by X-ray diffraction
2
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2
1
The ligand
L
is similar to
L
but contains a butyl spacer ligand strand forms a hydrogen bond to one of the fluoride
2
between the two amine-bidentate domains. Reaction of
with Cu(trif) in MeNO gives a tan coloured solution which Cu(II) metal ion (Fig. 5d). Examination of this material by ESI-
analysis by ESI-MS gives an ion at m/z 1391 and 620 which MS showed ions at m/z 1175 and m/z 1107 corresponding to
L
3
atoms on the -BF unit and the same fluoride coordinates the
2
2
2
+
2
2+
2
+
2
+
corresponds to {[Cu
2
(L
)
2
](trif)
3
}
and {[Cu
2
(
L
)
2
](trif)
2
}
{[Cu
2
(L
)
2
(O
2
P(OBF
3
)
2
)]}
and
2 2 3 3
{[Cu (L ) (O POBF )]}
respectively. Although we were unable to successfully grow respectively. Also present were smaller ions at 19 mass units
crystals of this species the ESI-MS data, coupled with higher at m/z 1194 and 1126 corresponding to
1
2
+
2
+
comparison with
L
, it seems likely a dinuclear species has {[Cu
2
(L
)
2
(HO
3
P(OBF
3
))](BF
4
)}
2 2 4 4
and {[Cu (L ) (HPO )](BF )} ,
been formed. Reaction of this species with Bu
4
NH PO gives a which we attribute to artefacts of the mass spectrometry
2
4
lime-green coloured solution from which a crystalline material process.
was deposited upon slow diffusion of diisopropyl ether.
b
a
Analysis by X-ray crystallography showed the expected
dinuclear structure with two Cu(II) metal ions coordinated by
two bidentate pyridyl-thiazole units from two different ligand
strands (Fig. 4). The phosphate anion bridges the two metal
ions coordinating each via two oxygen atoms and the Cu···O
coordination is supplemented by a single -NH···anion from
each ligand strand (Cu-N range 1.969(3) - 2.178(4) Å, Cu-O
d
c
2
.010(2) - 2.033(3) Å). The remaining amine and the phosphate
OH units form hydrogen bonding interactions with the triflate
counter anions. Again, in a similar fashion to the complex with
-
1
L
, the number of counter anions present shows that the
dihydrogen phosphate has not undergone further
deprotonation. ESI-MS analysis is consistent with the solid-
2
Figure 5. X-ray structure of [Cu
2
(
L
)
(O P(OBF
2 2
3
)
2
)](BF
3
) a) - c) showing the
2
+
) (H PO )](trif) } ,
state with ions observed at m/z 1339 {[Cu (
2
L
2
2
4
2
dinuclear assembly and d) partial view of the {Cu
2
(O
2
3 2
P(OBF ) )} core and the
2
+
m/z
[Cu2(
such as m/z 620 {[Cu(
1189
{[Cu (
L
) (HPO )](trif)}
2
and
m/z
520
2
4
hydrogen bonding to –NH atoms. The complex has crystallographically-imposed
inversion symmetry. Thermal ellipsoids shown at the 30% probability level.
Remaining tetrafluoroborate anions are omitted for clarity. Colour code: orange,
Cu(II); red, O; blue, N; yellow, S; lime F; grey, C; light orange, P; pink, B (apart
from 4c where the ligands have been coloured for clarity).
2
2+
{
L ) (HPO )]} as well as lower molecular weight species
2 4
2
+
)](trif)} .
L
The reaction in this manner is somewhat surprising as
tetrafluoroborate is
a
common anion for numerous
applications and is well-known for its chemical stability.
Reactions can occur at elevated temperatures and at high or
low pH and there is evidence that decomposition of this anion
can occur in ionic liquids and in the presence of reactive main
6
group compounds. However, decomposition of the BF ˉ anion
2
Figure 4. Two views of the X-ray structure of [Cu
2
(L
)
2
(H
2
PO
4
)](trif)
3
. Thermal
4
ellipsoids shown at the 30% probability level. Remaining triflate anions are
omitted for clarity. Colour code: orange, Cu(II); red, O; blue, N; yellow, S; lime F;
grey, C; light orange, P.
and reaction with phosphate is unprecedented, especially
7
considering the mild conditions. Furthermore, examination of
the CCDC shows that the phosphate–borane adducts (e.g.
(
RO) PO-BR ) are very rare and not derived from the reaction
3 3
2
Reaction of Cu(BF ) ·6H O with
4
L
and half an equivalent of
8,9
2
2
of phosphate and tetrafluoroborate.
dihydrogen phosphate in MeNO2 also gives a lime-green
solution from which crystals are deposited by slow diffusion of
diisopropyl ether. In the solid-state the dinuclear structure is
observed as expected. Each of the ligands partition into two
bidentate domains and coordinate different metal ions and the
phosphate anion bridges the two metal ions (Cu-N range
Quite why the BF ˉ anion reacts with phosphate in this manner
4
isn’t entirely clear. However, examination of the structure of
2
[Cu2(
L
) (H PO )](trif) shows that two of the triflate counter
2
2
4
3
ions are held close to the encapsulated phosphate anion by a
series of –POH····trif and –NH····trif interactions coupled with
Cu····O SCF interactions (ave. Cu····O 3.2 Å). It is possible that
3
3
1.974(5) - 2.204(6) Å, Cu-O 2.006(4) Å) in an identical manner
in the case of the analogous tetrafluoroborate salt the
resulting close proximity induces a reaction of the anion with
dihydrogen phosphate via either a dissociative (via a BF3
intermediate) or concerted mechanism, eliminating HF. It is
worth noting that, due to the more sterically demanding
to the previously described triflate structure (Fig 5a – 5c).
However, in this structure the phosphate has reacted with two
tetrafluoroborate anions to give a molecule of {BF
3
3
O-PO
2
-
OBF
3
} ˉ. This molecule is held within the self-assembly by two
Cu···O coordination bonds and a hydrogen bonding interaction
between one of the amine units on the ligand strand and a
phosphate oxygen atom. The remaining amine unit on each
environment imposed by the shorter ethylene spacer, in
1
[Cu
2
(
L
)
2
(H
2
PO
4
)](trif)
3
only one phosphate is held close to the
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dihydrogen phosphate and correspondingly the phosphate
unit can only react with one of the tetrafluoroborate anions.
3
(a) B. Hasenknopf, J-M. Lehn, N. Boumediene, E. Leize, and
A. Van Dorsselaer, Angew. Chem. Int. Ed., 1998, 37, 3265; (b)
B. Hasenknopf, J-M. Lehn, N. Boumediene, A. Dupont-
Gervais, A. Van Dorsselaer, B. Kneisel, and D. Fenske, J. Am
Chem. Soc., 1997, 119, 10956; (c) J. S. Wright, A. J. Metherell,
W. M. Cullen, J. R. Piper, R. Dawson and M. D. Ward, Chem.
Commun., 2017, 53, 4398; (d) W. Cullen, M. C. Misuraca, C.
A. Hunter, N. H. Williams and M. D. Ward, Nature Chem.,
2016, 8, 231; (e) D. Fujita, Y. Ueda, S. Sato, N. Mizuno, T.
Kumasaka and M. Fujita, Nature, 2016, 540, 563.
(a) J. W. Steed, Chem. Soc. Rev. 2009, 38, 506; (b) S. O. Kang,
J. M. Llinares, V. W. Day and K. Bowman-James, Chem. Soc.
Rev. 2010, 39, 3980; (c) P. A. Gale, E. N. W. Howe and X. Wu,
4
The formation of different structures upon reaction of BF ˉ
1
2
e.g. trinuclear in the case of L and dinuclear with L ) is a
(
consequence of the differing lengths of the aliphatic spacer.
1
3+
Reaction of [Cu
bonds reacting with BF
inclusion of the electronegative group (e.g. –OBF
2
(L
)
2
(H
2
PO
4
)] results in one of the (HO
3
P-OH)ˉ
2
4
ˉ giving initially (HO
3
P-OBF
3
) ˉ and the
) increases
3
the acidity of the phosphate unit. This increased acidity will
2
allow full deprotonation of the (HO P-OBF ) ˉ unit and
3 3
4
subsequently form three Cu···O coordination bonds, acting as a
central template for the formation of the trinuclear assembly.
However, because of the larger length of the butyl unit in
Chem. 2016, 1, 351; (d) N. Busschaert, S. Park, K. Baek, Y.
Choi, J. Park, E. Howe, J. Hiscock, L. Karagiannidis, I.
Marques, V. Felix, W. Namkung, J. L. Sessler, P. A. Gale and I.
Shin, Nature Chemistry, 2017, 9, 667; (e) P. Gale, J. Davis and
R. Quesada, Chem. Soc. Rev., 2017, 46, 2497; (f) P. Gale and
C. Caltagirone, Chem. Soc. Rev., 2015, 44, 4212; (g) N.
Busschaert, C. Caltagirone, W. Van Rossom and P. A. Gale,
Chem. Rev., 2015, 115, 8038; (h) J. Hiscock, M. Sambrook, N.
2
3+
[Cu
2
(
L
)
2
(H
2
PO
4
)] the less sterically demanding environment
ˉ,
allows reaction between two of the P-OH bonds and BF
4
3
precluding the potential templation effect of the (O
3 3
P-OBF ) ˉ
unit.
We have shown that ligands that contain two bidentate
pyridyl-thiazole domains, separated by either 1,2-
) spacer, form
dinuclear assemblies upon coordination with Cu(trif) (e.g.
Cu ](trif) ) and these can bind dihydrogen phosphate
anions. In the presence of BF ˉ the dihydrogen phosphate
reacts with this anion and forms a {(PO-BF )ˉ} fragment. In the
this reaction occurs twice to form the helicate
Wells and P. Gale, Chem. Sci., 2015,
6
, 5680; (i) M.
J.
a
Langton, C. J. Serpell and P. Beer, Angew. Chem. Int. Ed.
2016, 55, 1974; (j) J. L. Sessler, P. A. Gale and W.-S. Cho,
Anion Receptor Chemistry, RSC, Cambridge, 2006. N. H.
Evans and P. D. Beer, Angew. Chem. Int. Ed., 2014, 53,
1
2
diaminoethyl (L ) or 1,4-diaminobutyl (L
2
[
2
L
2
4
1
1716. A. Bessette, S. Nag, A. K. Pal, S. Derossi and G. S.
4
Hanan, Supramolecular Chemistry, 2012, 24, 595. A. L.
Blackburn, N. C. A. Baker and N. C. Fletcher, RSC Adv., 2014,
4, 18442.
3
2
case of
L
2
+
1
species [Cu
2
(L
)
2
(O
2
P(OBF
3
)
2
)] . With
L
, which contains the
5
(a) R. Custelcean, Chem. Soc. Rev. 2014, 43, 1813; (b) P.
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shorter ethylene spacer, the phosphate only reacts once but
the structure reassembles to form a trinuclear circular helicate
1
3+
[
3 3 3 3
Cu (L ) (O POBF )] .
Conflicts of interest
There are no conflicts to declare.
Notes and references
‡ Footnotes relating to the main text should appear here. These
might include comments relevant to but not central to the
matter under discussion, limited experimental and spectral data,
and crystallographic data.
§
6
For hydrolysis of tetrafluoroborate in ionic liquids see: M. G.
Freire, C. M. S. S. Neves, I. M. Marrucho, J. A. P. Coutinho,
and A. M. Fernandes J. Phys. Chem. A 2010, 114, 3744. For
§§
etc.
1
reactions with (SiMe
3
)
Am. Chem. Soc. 2013, 135
2
see: J. M. Larsson and K. J. Szabó, J.
443. S.Radosavljević,
J. -M. Lehn, Supramolecular Chemistry, VCH, Weinheim,
995; J.W. Steed, J. L. Atwood, Supramolecular Chemistry,
John Wiley and Sons, Chichester, 2000.
,
1
V.Ŝćepanović, S.Stević and D.Milojković, J. Fluorine Chem.,
1979, 13, 465.
Hydrolysis of BF ˉ to (BF OH)ˉ has been observed with Cu(II)
2
(a) M.J. Hannon, L.J. Childs, Supramol. Chem., 2004, 167; (b)
M. Albrecht, Chem. Rev. 2001, 101, 3547; (c) M. Albrecht,
Chem. Soc. Rev., 1998, 27, 281; (d) C. Piguet, G. Bernardinelli,
G. Hopfgartner, Chem. Rev., 1997, 97, 2005; (e) E.C.
Constable, in Comprehensive Supramolecular Chemistry, vol.
7
8
4
3
see: J. C. Dewan and L. K. Thompson, Can. J. Chem., 1982, 60
121.
,
Whilst adducts between phosphine oxides and borates are
known (e.g. R P-O-BR ) to the best of our knowledge there is
3
3
9; Polynuclear Transition Metal Helicates, ed J.-P. Sauvage,
Elsevier, Oxford, 1996, pp. 213; (f) B. Jana, L. Cera, B. Akhuli,
S. Naskar, C. A. Schalley and P. Ghosh, Inorg. Chem., 2017,
3 3
only one report of compounds containing the (RO) PO-BR
unit see: A. Styskalik, M. Babiak, P. Machac, B. Relichova and
J. Pinkas, Inorg. Chem. 2017, 56, 10699
Reactions between phosphate and boric acid are well
56, 12505; (g) S. J. Allison, D. Cooke, F. S. Davidson, P. I. P.
9
Elliott, R. A. Faulkner, H. B. S. Griffiths, O. J. Harper, O.
Hussain, P. J. Owen-Lynch, R. M. Phillips, C. R. Rice, S. L.
Shepherd and R. T. Wheelhouse, Angew. Chem. Int. Ed.,
established and boron phosphate (BPO ) is known from the
4
reaction of phosphoric acid with boric acid see: F. Mylius and
A. Meusser, Berichte der deutschen chemischen Gesellschaft.
1904, 37, 397.
2
018, DOI: 10.1002/anie.201805510.
4
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C8CC04900A
Dihydrogen Phosphate-containing Dinuclear Double
Assemblies that Demonstrate Phosphate Reactivity to the
Tetrafluoroborate Anion.
Robert A. Faulkner, Nathan J. Patmore, Craig R. Rice* and Christopher Slater.
Department of Chemical and Biological Sciences, University of Huddersfield, Huddersfield,
HD1 3DH. Fax: +44 (0) 148-447-2182; Tel: +44 (0) 148-447-3759; E-mail:
b
c.r.rice@hud.ac.uk.
Table of Contents entry.
1
2
The ligands L and L both form dinuclear assemblies with Cu(II) and these react with
dihydrogen phosphate so that the anion is incorporated within the assembly (e.g.
3
+
[
Cu
2 2 2 4
L (H PO )] ). However, in the presence of tetrafluoroborate anions the phosphate
1
3+
undergoes
[
reaction
Cu (L ) (O P(OBF ) )] .
2 2 2 3 2
with
the
anion
forming
[Cu
3
(L )
3
(O
3
POBF
3
)]
and
2
+