Molecular tectonics: Heterometallic (Ir,Cu) grid-type coordination networks based on cyclometallated Ir(III) chiral metallatectons

Article abstract of DOI:10.1039/c5cc06427a

A chiral-at-metal Ir(iii) organometallic metallatecton was synthesised as a racemic mixture and as enantiopure complexes and combined with Cu(ii) to afford a heterobimetallic (Ir,Cu) grid-type 2D coordination network.

Full text of DOI:10.1039/c5cc06427a

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Molecular tectonics: heterometallic (Ir,Cu) grid-type coordination
networks based on cyclometallated Ir(III) chiral metallatectons
Chaojie Xu,a Aurélie Guenet,*a Nathalie Kyritsakas,a Jean-Marc Planeix*a and Mir Wais Hosseini*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
chiral-at-metal Ir(III) organometallic metallatecton was enantiomers, rac
synthesised as a racemic mixture and as enantiopure complexes [Ir(ppy)2( )][PF6]) or
and combined with Cu(II) to afford a heterobimetallic (Ir,Cu) grid- (Scheme 1). Furthermore, we describe the formation of a
-
[Ir(ppy)2(
1
)][PF6], and as enantiopure
Λ (Λ-
1
ꢀ
(
ꢀ
-[Ir(ppy)2( )][PF6]) complexes
1
type 2D coordination network.
heterometallic (Cu,Ir) 2D grid-type coordination network
resulting from the combination of rac-[Ir(ppy)2(1)][PF6] and
Molecular chirality in coordination compounds and
organometallic complexes1 may be centred on the metal, on
the ligand or on both entities. While chiral-at-metal complexes
have been employed in homogeneous asymmetric catalysis,2
the use of such complexes in extended architectures such as
coordination networks3 has not been fully exploited.4
Coordination networks, also known as coordination polymers
or MOFs, are extended periodic architectures resulting from
the bridging of consecutives organic entities by metal centres.5
The design of such solid-state crystalline materials may be
achieved using the molecular tectonics approach.6 Using self-
assembly processes, the generation of coordination networks
takes place between programmed organic coordinating
tectons and metal centres or complexes behaving as
connecting nodes. Homochiral coordination networks based
on the use of enantiopure organic tectons have been
reported.7-8 Chiral coordination complexes bearing peripheral
coordinating sites and thus behaving as metallatectons9 have
also been used for the formation of homochiral heterometallic
networks.7a-d, 10 However, for the reported architectures, the
chirality originates from the organic part (mainly BINAP, BINOL
or salen-type ligands). Thus, the design and formation of
chiral-at-metal coordination networks based on chiral
octahedral tris-chelate metallatectons remains a challenge.
Herein, we report the synthesis and characterisation in
solution and in the solid state of an unprecedented
[Cu(CH3CN)4][BF4].
Scheme 1 Synthetic routes for the preparation of a) ligand 1 and b) [Ir(ppy)2(1)][PF6] as
a racemate, rac-[Ir(ppy)2(1)][PF6], and enantiomerically pure ꢀ-[Ir(ppy)2(1)][PF6].
Synthesis of Λ-[Ir(ppy)2(1)][PF6] was performed using D-serine instead of L-serine. The
chloride salts of the racemic mixture as well as the enantiopure complexes can be
isolated before performing the last metathesis step using KPF6 (step ii) 2)).
cyclometalated
Ir(III)
complex-based
metallatecton
and
[Ir(ppy)2(1)][PF6] as a racemic mixture of both
Λ
ꢀ
We propose to use chiral-at-metal metallatectons to generate
homochiral heterometallic coordination networks. The chiral
metallatecton is based on an achiral bipyridyl chelate (bpy)
bearing two peripheral monodentate pyridyl coordinating
sites. The chirality, of the
Λ
and
ꢀ
type, is introduced through
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the binding by the chelate moiety of a chiral octahedral metal All three chelating ligands are almost planar (average dihedral
complex offering two free coordination sites. In order to angle N-C-C-N of ca. -0.322° for the bpy and N-C-C-C angle in
prevent epimerisation or racemisation, a cyclometallated Ir(III) the range -6.480 to 1.956° for ppy). The ethynyl spacers are
complex was chosen as configurationally stable entity. Thus, almost linear (C-C-C angles in the 175.36-179.02° range) and
the chiral cationic metallatecton [Ir(ppy)2(
The latter combines the organic tecton , based on the 2,2’- expected, both
bipyridine backbone equipped at positions 5 and 5' with two interactions between adjacent complexes are observed in
1
)]+ was designed. the terminal pyridyl units almost coplanar to the bpy unit. As
and enantiomers are present in the crystal.
1
ꢀ
Λ
π-π
pyridyl units connected through ethynyl spacers using the crystal lattice (see ESI). Finally, the length of the
positions 4 and 4', with Ir(III) centre complexed by two 2- metallatecton, i.e. the distance between the two terminal N
phenylpyridine (ppy) moieties. The ethynyl spacer was used to atoms, is ca. 20.6 Å. Both pure ꢀ- and Λ-[Ir(ppy)2(1)][Cl]
extend conjugation of the tecton The choice of enantiomers crystallize in the P21212 chiral space group. The
1
.
a
cyclometallated Ir(III) complex was based on its rich geometrical parameters observed for both enantiomers (see
photophysical properties.11
ESI) are similar to those obtained for the racemic mixture.
The synthesis of the chiral Ir metallatecton [Ir(ppy)2(1
)]+ is
based on the precursor tecton
obtained in four steps (37
protection/deprotection and coupling reactions. Starting from
5-bromo-2-iodopyridine, compound was obtained in three
steps (51 % overall yield).12 A Pd-catalyzed Sonogashira
coupling reaction between and 4-iodopyridine afforded the
tecton in 72 % yield (see ESI). The Ir(III) complex (rac-
[Ir(ppy)2( )][PF6]), as a mixture of and enantiomers, was
prepared in 85 % yield (see ESI) by reaction of the dichloro-
bridged Ir(III) dimer rac-[Ir(ppy)2(µ-Cl)]213 with (Scheme 1b).14
For the synthesis of the two enantiopure complexes ( - and
[Ir(ppy)2( )][PF6]), chiral resolution of the Ir(III) dimer was
achieved using L or D-serine as chiral auxiliaries (Scheme 1b).15
The two ꢀꢀ and ΛΛ-[Ir(ppy)2(μ-Cl)]2 enantiomers were
obtained in 43 and 48 % yields respectively. The final
enantiopure metallatectons - and -[Ir(ppy)2( )][A] (A = Cl or
PF6) were obtained upon reaction of ꢀꢀ- or ΛΛ-[Ir(ppy)2(μ-
Cl)]2 dimer with . Both enantiomers were isolated as their
chloride salts (74 % and 76 % for the and the enantiomers
respectively). They were converted into their PF6 salts by
metathesis with KPF6 in water (80 % and 83 % yield for the
and enantiomers respectively). The two chiral complexes
1
(Scheme 1a). The latter was
%
overall yield) using
4
Fig. 1 Crystal structure of rac-[Ir(ppy)2(1)][PF6]. Solvent molecules, H atoms and PF6
4
anions have been omitted for clarity. For bond distances and angles see ESI.
1
1
Λ
ꢀ
The photophysical properties of the metallatecton as
a
racemic mixture were studied in the solid state (Fig. 2) and in
solution (see ESI). In solution, the Ir(III) complex exhibits an
intense absorption band between 240 and 400 nm attributed
to spin-allowed LC transitions involving the ppy and the bpy
moieties with a contribution of MLCT and LLCT transitions as
previously described for analogous compounds.17a The
relatively intense absorption band around 300-360 nm is
1
ꢀ
Λ-
1
-
ꢀ
Λ
1
probably due to π-π* transitions and conjugation over the bpy
moieties as already observed on similar complexes.19 In the
solid state, a strong absorption band between 250 and 700 nm
arising from LC, MLCT and LLCT transitions is observed. The
emission spectra recorded for rac-[Ir(ppy)2(1)][PF6] in the solid
state (Fig. 2) and in degassed THF (see ESI) shows an
unstructured broad band with a maximum at ca. 677 nm (695
nm in degassed THF), characteristic of charge transfer
electronic transitions. As for the analogous compound
[Ir(ppy)2(bpy)][PF6], the emission may be attributed to a
1
ꢀ
Λ
ꢀ
Λ
were characterised by standard techniques (see ESI) and by
circular dichroism (CD). As expected, the enantiomers exhibit
mirror images CD spectra and opposite specific rotation ([α]D).
The racemic mixture as well as enantiopure metallatectons
mixture of 3MLCT (Ir
transitions.17a, 20
→bpy) and 3LLCT (ppy→bpy)
were characterised by X-ray diffraction on single crystals (see
ESI). Single crystals of the racemate rac-[Ir(ppy)2(
obtained by vapour diffusion of Et2O into a CH3CN solution of
rac-[Ir(ppy)2( )][PF6] (Fig. 1). For the enantiopure chloride salts
- and -[Ir(ppy)2( )][Cl], single crystals could be obtained for
1)][PF6] were
1
ꢀ
Λ
1
both enantiomers upon slow diffusion of toluene into a 1/1
toluene/CH3CN solution of the desired complex (see ESI)
confirming the absolute configuration of the enantiomers. For
all three crystals, owing to the severe disorder of solvent
molecules, the SQUEEZE command16 was used to remove the
corresponding electron density and solve the structure. rac-
Fig. 2 Diffuse reflectance (solid) and emission (dotted) spectra for rac-[Ir(ppy)2(1)][PF6]
in the solid state (λexc = 450 nm).
[Ir(ppy)2(1)][PF6] crystallizes in the triclinic system (P-1). The
geometrical parameters (see ESI) are similar to those reported
for similar Iridium(III) complexes containing ppy and bpy
ligands.17 The Ir center adopts a slightly distorted octahedral
geometry with the expected trans- and cis-arrangement of N
and C atoms of the cyclometallated ligand respectively.11b, 18
The bathochromic shift observed when compared to
[Ir(ppy)2(bpy)][PF6]
attributed to delocalisation of the bipyridine
(λ
em = 590 nm, RT, THF)19a may be
π
stabilizing the LUMO as described in solution for ppy-
system,
cyclometalated Ir complexes bearing 2,2’-bipyridine ligand
2 | J. Name., 2012, 00, 1-3
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substituted in positions 5 and 5’ with aryl moieties17c or Furthermore, unlike what has been observed before for
oligo(arylene ethynylene) units.19a, 19c Finally, in the solid state, another grid-like heterometallic coordination network,21 each
a quantum yield (QY) of 3 % was determined. This relatively grid is chiral as only one of the two enantiomers is present
weak QY might be related to the presence of
π
as evidenced in the crystal structure, quenching partially the staggered fashion along the c axis with alternation of
-
π
interactions, (Fig. 3b). The consecutive homochiral sheets are packed in a
and
ꢀ
Λ
solid state emission. It should be noted that the PXRD pattern chirality leading thus to a non-chiral crystal. The inter-sheet
of the sample used for the luminescence measurements distance (distance between two mean planes defined by two
matches the simulated pattern from single crystal structural consecutive grids) is 6.21 Å (see ESI). Owing to the acentric
data (see ESI). Unfortunately, owing to its rather photo- nature of the metallatecton [Ir(ppy)2(
instability in solution, QY value could not be determined 2D network, Ir(III) centres may be oriented inwardly (i) or
accurately. outwardly (o). Thus, for a single grid, four arrangements (i4, i3o,
1
)]+, within the grid type
The formation of extended heterometallic coordination ioio and iioo) are possible (Fig. 4 a-d). Furthermore, for the iioo
networks was explored by combining the Ir(III)-based arrangement (Fig. 4d), two types of polar sheets may be
metallatectons with different metal salts. Only the formed (Fig. 4 e and f). For the heterometallic (Ir,Cu) grid-type
combination of the racemic mixture rac-[Ir(ppy)2(1)][PF6] and a architecture discussed above, each sheet is polar (Fig. 4e).
Copper salt afforded single crystals. Indeed, upon slow However, consecutive sheets are packed in a head-to-tail
diffusion of an EtOH solution of [Cu(CH3CN)4][BF4] into a CHCl3 fashion (centrosymmetric packing) leading thus to an apolar
solution of rac-[Ir(ppy)2(1)][PF6], red crystals were obtained crystal.
after a few days. Structural studies by X-Ray diffraction on
single crystal revealed that the crystal (space group C2/c) was
-
-
composed of [Ir(ppy)2(1
)]+, Cu2+ cation, BF4 and PF6 anions
and solvent molecules (CHCl3, EtOH). Owing to the important
disorder of other solvent molecules, the SQUEEZE command16
was employed to process the data. It appears that Cu(I) was
oxidized to Cu(II) during the crystallisation process taking place
in the presence of air. The structural investigation revealed the
formation of a grid-type network (Fig. 3). The Iridium complex
within the 2D network exhibits similar geometrical parameters
(average bond lengths and angles: Ir-Cppy 2.00 Å, Ir-Nppy 2.04 Å,
Ir-Nbpy 2.13 Å, Nppy-Ir-Nppy 174.6°, Nppy-Ir-Cppy 81.0°, Nbpy-Ir-Nbpy
76.5°) as those observed for the discrete metallatecton.
Fig.4 Schematic representations of all four possibilities a (i4), b (i3o), c (ioio) and d (iioo)
with I and o in and out positioning of the iridium centre within the grid. Green and
yellow spheres represent the 4-connecting Cu node and chiral Ir complex respectively.
In the case of d (iioo), two possibilities of translation lead to polar organisations (e and
f).
However, while in the crystal structure of rac-[Ir(ppy)2(1)][PF6],
the terminal pyridyl units were almost coplanar to the
backbone, here, they are tilted with respect to the bpy ligand
(tilt angles of -77.74° and -31.10°). The Cu(II) centre adopts a
slightly distorted octahedral geometry with four pyridyl units
belonging to four different metallatectons occupying the
Unfortunately, crystals were found to be rather air-unstable
and thus no proper match between observed and simulated
patterns could be obtained by PXRD study (see ESI).
Degradation in less than an hour of the single crystals was also
observed using an optical microscope. This might be due to
desolvation and collapse of the architecture.
-
square base of the octahedron (Cu-N ca. 2.01 Å) and two BF4
anions in axial positions (Cu-F 2.377(5) Å; F-Cu-F 176.0(2)° and
N-Cu-F in the 85.7(2)°-91.7(2)° range). Within the 2D-network,
two consecutive Cu(II) nodes are separated by 24.44 Å.
Preliminary photoluminescence measurements (see ESI, page
S3) in the solid state under ambient conditions were carried
out on a standard fluorimeter. Unfortunately, no emission of
the coordination network could be detected. The
luminescence quenching is probably due to the presence of
the paramagnetic Cu(II) cation22 or to intermolecular
interactions. O2 quenching may also be expected as previously
described.23 Because of the air instability of crystals, further
studies in view of rationalising the emission quenching could
not be carried out.
In conclusion, chiral-at-metal bis-cyclometalated cationic Ir(III)
complexes bearing 5,5’-substituted 2,2’-bipyridine as third
ligand were synthesised both as a racemic mixture and as
enantiomerically pure species and characterised in particular
in the solid state by X-ray diffraction on single crystals. The
Fig. 3 Portions of the crystal structure of rac-Ir(ppy)2(1)⋅Cu(BF4)2 showing the grid type
architecture resulting from the interconnection of the ꢀ-Ir metallatecton with Cu(BF4)2
acting as metallic nodes (a) and the staggered packing of two consecutive chiral grids
along the c axis (b). The chiral grid composed of Λ enantiomers is depicted in red and
the one with the ꢀ enantiomers in blue. Solvent molecules, H atoms and PF6 anions
have been omitted for clarity.
combination of the racemic mixture of
Λ and ꢀ enantiomers
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M. W. Hosseini, Chem. Commun., 2013, 49, 4468-4470; (e) N.
Marets, V. Bulach and M. W. Hosseini, New J. Chem., 2013,
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behaving as a chiral metallatecton with Cu(II) acting as a 4-
connecting node resulted in the formation of an achiral
heterobimetallic
grid-type
coordination
network.
Unfortunately, the crystalline material appeared to be rather
unstable outside the mother liquor. With the aim of generating
stable homochiral and luminescent coordination networks,
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This contribution is part of an international research project,
Chiranet, funded by the European Regional Development Fund
(ERDF) under the INTERREG IV Upper Rhine Programme and as
part of the Science Offensive of the Trinational Upper Rhine
Metropolitan Region. Financial support from the University of
Strasbourg, the International Centre for Frontier Research in
Chemistry (icFRC), Laboratory of excellence LabEx CSC,
Strasbourg, the Institut Universitaire de France, the CNRS is
acknowledged.
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DOI: 10.1039/C5CC06427A
Journal Name
COMMUNICATION
Graphical Abstract
The combination of
a Chiral-at-metal Ir(III) organometallic
metallatecton with Cu(II) leads to the formation of
heterobimetallic (Ir,Cu) grid type 2D coordination network.
a
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