Luminescent 1D- and 2D-Coordination Polymers Using CuX Salts (X = Cl, Br, I) and a Metal-Containing Dithioether Ligand

Article abstract of DOI:10.1021/acs.inorgchem.6b01703

The organometallic synthon trans-[p-MeSC₆H₄C≡C-Pt(PMe₃)₂-C≡CC₆H₄SMe] (L1) reacts with CuX (X = Cl, Br, I) in PrCN and PhCN to form 1D- or 2D-coordination polymers (CP) with a very high degr

Full text of DOI:10.1021/acs.inorgchem.6b01703

Article
pubs.acs.org/IC
Luminescent 1D- and 2D-Coordination Polymers Using CuX Salts (X =
Cl, Br, I) and a Metal-Containing Dithioether Ligand
Frank Juvenal, Adam Langlois, Antoine Bonnot, Daniel Fortin, and Pierre D. Harvey*
́ ́ ́
Departement de chimie, Universite de Sherbrooke, Sherbrooke, Quebec, Canada J1K 2R1
S
* Supporting Information
ABSTRACT: The organometallic synthon trans-[p-MeSC6H4CC-
Pt(PMe3)2-CCC6H4SMe] (L1) reacts with CuX (X = Cl, Br, I) in
PrCN and PhCN to form 1D- or 2D-coordination polymers (CP)
with a very high degree of variability of features. The copper-halide
unit can be either the rhomboids Cu2X2 fragments or the step cubane
Cu4I4. The CP’s may also incorporate a crystallization solvent
molecule or not, which may be coordinated to copper or not. Their
characterizations were performed by X-ray crystallography, thermal
gravimetric analysis (TGA), and IR, absorption, and emission spectra
as well as photophysical measurements in the presence and absence of
solvent crystallization molecules. The nature of the singlet and triplet excited state was addressed using DFT and TDDFT
computations, which turn out to be mainly ππ* with some minor MLCT (Cu4I4 → L1) contributions. The porosity of the
materials has been evaluated by BET (N2 at 77 K). The solvent-free 1D CP’s are not prone to capture solvent molecules or CO2,
but the efficiency for CO2 absorption is best for the 2D CP, which exhibits the presence of clear cavities in the grid structure, after
the removal of the crystallization molecules.
with copper halide salts (X = Cl, Br, I) demonstrated a clear
accentuated ability to form 1D- (frequent), 2D- (often), and
3D- (scarce) coordination polymers dominantly of the type
(Cu2X2)n(thioether)m (n = 1−4; m = n or n − 1).15 In
relevance with this work, a recent review focused exclusively on
2D-materials (55 structures).16 Because of the rigidity of the
[Pt]-frame, there is also an opportunity to form 3D-
frameworks.17
We now report a new rigid dithioether ligand, trans-[p-
MeSC6H4CCPt(PMe3)2CC-p-C6H4SMe] (L1) along with
its coordination polymers built upon CuX salts (X = Cl, Br, I)
prepared in PrCN and PhCN, generating six different ([Pt]-
[Cu])n CP’s (Chart 2). These new CP’s can be either 1D or
2D, may include a solvent crystallization molecule in the unit
cell or not, and may be or not coordinated to a Cu atom. The
photophysical properties were investigated in some detail
before and after removing the crystallization solvent molecule.
The assignment for the emissive excited state was performed
with the aid of the emission signatures (Stoke shift and
emisison lifetimes) and DFT and TDDFT computations.
Finally, the porosity of the CP’s and amount of adsorption of
CO2 were measured where a direct relationship between these
parameters was observed.
INTRODUCTION
■
The organometallic synthons trans-Pt(CC)2(PR3)2 ([Pt]; R
= aryl, achiral, or chiral alkyl)1 and M−M-bonded
Pt2(dppm)2(CC)2 ([Pt2]; dppm = (Ph2P)2CH2)2) are
known to respectively form moderately and strongly conjugated
polymers (Chart 1). The relative amplitude of electronic
coupling between the anchoring groups attached to the ethynyl
functions are well-known from electrochemical investigations,
using redox-active ferrocenyl probes,3 and from photophysical
measurements.2b The redox and optically active [Pt]-containing
polymers share a common structure, ([Pt]-G)n, where G is
most of the time an organic fragment,1 which found
applications in 2-photon absorption,4 solar cells,5 and light
emitting diodes.6 However, the cases where G is either
composed of organometallic residues or coordination moieties
are far more scarce. This short list can be divided into four
categories: G is included in the inner core of the polymer
(germanium-7 and iridium-containing unit,8 zinc(II)-
porphyrin9), as a side group anchored onto the ethynyl bond
(via coordinating Cu-10 or Ag-complexes11), attached as a
pendent group (here ferrocenyl) linked to either the
phosphine12 or the organic residue,13 and as used as end
group.14 Many of these heterobimetallic polymers have been
investigated for their luminescence properties7−9 and electro-
chemical activities.8,13 The common feature is that these
polymers are all 1D-materials.
EXPERIMENTAL SECTION
■
Materials. CuI, CuBr, and CuCl were purchased from Aldrich. 4-
(Trimethylsilylethynyl)thioanisole and cis-dichlorobis-
There is an opportunity to exploit the chemistry of the
already established coordination of the ethynyl group and to
incorporate a supplementary function in order to promote the
formation of 2D-materials. In this respect, the use of thioether
Received: July 20, 2016
© XXXX American Chemical Society
A
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a
Chart 1. Selected Examples of Structures of the Heterobimetallic [M]-[Pt]-Containing Polymers
a
All these polymers are 1D-materials.
C, 37.17; H, 3.87; N, 2.30%. IR (cm−1): 2987, ν(CH); 2883, ν(CH);
2107, ν(CC); 1650, ν(CC).
Chart 2. Structures of the Heterobimetallic [Pt]-[Cu]-
Containing Polymers
a
Synthesis of {[Cu4Cl4L1]·PrCN]}n (CP3). L1 (20.0 mg, 0.031 mmol)
and CuCl (6.0 mg, 0.062 mmol) were dissolved in 5 mL of
butyronitrile under argon. The mixture was stirred for 2 h in a vial at
room temperature and slightly heated it to completely dissolve. Slow
cooling the solution at room temperature gave clear pale yellow prism-
like crystals and were isolated by filtration of the solution. Yield: 48%.
Anal. Calcd for C52H71Cl4Cu4NP4Pt2S4 (1748.36): C, 35.68; H, 4.06;
N, 0.80%. Found: C, 35.38; H, 4.16; N, 0.72%. IR (cm−1): 2970,
ν(CH); 2907, ν(CH); 2106, ν(CC); 1590, ν(CC).
Synthesis of {[Cu2Cl2L1]·PhCN]}n (CP4). L1 (20.0 mg, 0.031 mmol)
and CuCl (6.0 mg, 0.062 mmol) were dissolved in 5 mL of
benzonitrile under argon. The resulting mixture was stirred for 2 h in a
vial at room temperature and slightly heated it to completely solubilize.
The solution was slowly cooled at room temperature to give clear pale
yellow prism-like crystals which were isolated by filtration. Yield: 44%.
Anal. Calcd for C31H37Cl2Cu2NP2PtS2 (942.75): C, 39.45; H, 3.92; N,
1.48%. Found: C, 40.21; H, 4.13; N, 1.67%. IR (cm−1): 2983, ν(CH);
2894, ν(CH); 2106, ν(CC); 1586, ν(CC).
a
These polymers are either 1D- or 2D-materials.
(trimethylphosphine)platinum(II) were prepared according to a
known procedure.18b,c Details for this synthesis are placed in the SI
for convenience. The synthesis of cis-(PMe3)2PtCl2 to form the trans-
compound has previously been reported.18c
Synthesis of L1. cis-Dichlorobis(trimethylphosphine)platinum(II)
(0.498g, 1.18 mmol) and 4-ethynylthioanisole (0.480 g, 3.24 mmol)
were added to a round-bottom flask. 50:50 distilled THF/NHEt2 was
added (10 mL: 10 mL), and the mixture was degassed with argon and
stirred for 30 min. CuI (0.004 g, 0.02 mmol) was added, and the
mixture was degassed with argon. The solution was left stirring at
room temperature for 24 h and was placed in the fridge to settle. The
product was filtered and washed with cold water and cold methanol.
Synthesis of {[Cu4Br4L1]}n (CP5). L1 (20.0 mg, 0.031 mmol) and
CuBr (9.0 mg, 0.062 mmol) were dissolved in 5 mL of butyronitrile
under argon. The mixture was then stirred for 2 h in a vial at room
temperature and slightly heated it to completely dissolve. The solution
was slowly cooled at room temperature to give clear light yellow
prism-like crystals. Yield: 52%. Anal. Calcd for C48H64Br4Cu4P4Pt2S4
(1857.09): C, 31.01; H, 3.45%. Found: C, 30.92; H, 3.59%. IR (cm−1):
2970, ν(CH); 2894, ν(CH); 2106, ν(CC); 1594, ν(CC).
Synthesis of {[Cu2Br2L1]}n (CP5′). L1 (20.0 mg, 0.031 mmol) and
CuBr (9.0 mg, 0.062 mmol) were dissolved in 5 mL of benzonitrile
under argon. The mixture was then stirred for 2 h in a vial at room
temperature and slightly heated it. The solution was slowly cooled at
room temperature to give clear light yellow prism-like crystals Yield:
50%. Anal. Calcd for C48H64Br4Cu4P4Pt2S4 (1857.09): C, 31.01; H,
3.45%. Found: C, 30.78; H, 3.70%. IR (cm−1): 2973, ν(CH); 2901,
ν(CH); 2106, ν(CC); 1598, ν(CC).
1
Finally, the product was dried. Yield 0.664 g (87%). H NMR (300
MHz, CD2Cl2) δ 7.21 (d, J = 8.4 Hz, 4H), 7.10 (d, 4H), 2.46 (s, 6H),
1.82−1.64 (m, 18H). 31P NMR (122 MHz, CDCl3): δ −20.46 (s, JPt−P
= 2299 Hz). Anal. Calcd for C24H32P2PtS2: C, 44.88; H, 4.99%.
Found: C, 44.97; H, 4.86%.%. IR (cm−1): 2979, ν(CH); 2902, ν(CH);
2108, ν(CC); 1653, ν(CC).
Synthesis of {[Cu4I4L1]·PrCN]}n (CP1). L1 (20.0 mg, 0.031 mmol)
and CuI (12.0 mg, 0.062 mmol) were dissolved in 5 mL of
butyronitrile. The solvent was degassed under argon prior to the
reaction and the resulting mixture was stirred for 2 h in a vial at room
temperature. The mixture was slightly heated and allowed to cool at
room temperature, which facilitated the crystals formation. The
crystals were isolated by filtering the solution. Yield: 58%. Anal. Calcd
for C14H19.50Cu2I2N0.5PPt0.50S (736.26): C, 22.81; H, 2.65; N, 0.95%.
Found: C, 23.03; H, 2.86; N, 1.04%. IR (cm−1): 2970, ν(CH); 2907,
ν(CH); 2106, ν(CC); 1586, ν(CC).
Gas Sorption Isotherm Measurements. Gas sorption isotherms
at low-pressure ranging between 0 to 1100 mbar (∼1.1 atm) were
measured using a Micrometrics instrument Accelerated Surface Area
and Porosimetry (ASAP 2020) analyzer. For the isotherms, warm and
cold free space correction measurements were performed using
ultrahigh purity He gas with 99.999% purity. All gases used are of high
grade with purity of 99.999% for N2 gas and the purity grade of
Synthesis of {[Cu2I2L1]·PhCN]}n (CP2). Yield: 51%. Anal. Calcd for
C38H42Cu2I2N2P2PtS2 (1228.77): C, 37.10; H, 3.45; N, 2.28%. Found:
B
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a
Scheme 1. Synthesis of L1, and CP1-5′
a
Conditions: (i) cis-PtCl2(PMe3)2, CuI, Et2NH.
99.99% for CO2 gas. The measurements were done at different
temperatures of 77 K for N2 gas, while for CO2 gas, the measurement
was done at 273 K. Before performing the sorption measurements, the
samples were heated under a vacuum at 110 °C for approximately 8 h,
and the mass was measured. Then, the samples were backfilled with N2
and transported to the analysis port where further evacuation was done
for 2 h before starting the whole analysis. The surface area and pore
volumes were calculated by Brunauer−Emmett−Teller (BET)19,20 and
Density Functional Theory (DFT)21 models for N2 and CO2,
respectively.
Instruments. Solid state UV−vis spectra were recorded on a
Varian Cary 50 spectrophotometer at 298 K and 77 K using a raised-
angle transmittance apparatus and a homemade 77 K sample-holder.
Steady state fluorescence and excitation spectra were measured on an
Edinburgh Instruments FLS980 phosphorimeter equipped with single
monochromators. All samples were fished out as single crystals under
the microscope and were crushed prior to use. The identity of the
material was confirmed by comparing the calculated powder XRD
from the single crystal data with the experimental ones. The steady
state fluorescence spectra were recorded using a capillary. These
spectra were corrected for instrument response. Phosphorescence
lifetime measurements were made with an Edinburgh Instruments
FLS980 phosphorimeter equipped with “flash” pulsed lamp. The
frequency of the pulse can be adjusted from 1 to 100 Hz. All lifetime
values were obtained from deconvolution and distribution lifetime
analysis. The latter instrument was also used to measure the
chromaticity. The quantum yield measurements were performed
with the Horiba Fluorolog III. This instrument is equipped of an
integration sphere which allows the direct measurements of emission
quantum yields. The TGA traces were acquired on a PerkinElmer
TGA 7 apparatus in the temperature range between 20 and 950 °C at
10 °C/min under argon atmosphere. The figures have been treated by
Origin software.
with SBKJC effective core potentials were used for all Cu, I, Br, Cl, and
Pt atoms.32−35 The calculated absorption spectra were obtained from
GaussSum 3.2.36 Because these calculations are done to figure out the
electronic properties of these samples at solid state, the solvent effect
may not be considered.
X-ray Crystallography. A clear light yellow needle-like single-
crystal of L1 was measured on a Bruker Apex DUO system equipped
with a Cu Kα ImuS microfocus source with MX optics (λ = 1.54186
Å). On the other hand, clear light yellow prism-like single-crystals of
CP1, CP2, CP3, CP4, CP5, and CP5′ were measured on a Bruker
Kappa APEX II DUO CCD system equipped with a TRIUMPH
curved crystal monochromator and a Mo fine-focus tube (λ = 0.71073
Å). Diffraction data were recorded at 173 K for L1, CP1, CP2, CP3,
CP4, CP5, and CP5′. A total of 1727 frames were collected for L1
while 797 frames were collected for CP1, CP2, CP3, CP4, CP5, and
CP5′. The frames were integrated with the Bruker SAINT37 Software
package using a narrow-frame algorithm for all CPs and using the
wide-frame alogarithm for L1. Data were corrected for absorption
effects using the multiscan method (SADABS).37 The structures were
solved and refined using the Bruker SHELXTL Software Package using
space group P121/c1, with Z = 2 for L1, space group P1 with Z = 2 for
̅
CP1, CP3, and CP4, space group P1 with Z = 1 for CP5, and space
group P1 with Z = 1 for CP2 and CP5′. All non-hydrogen atoms were
̅
refined with anisotropic thermal parameters. The hydrogen atoms
were placed in calculated positions and were included in the final
refinement in a riding model with isotropic temperature parameters set
to Uiso(H) = 1.5Ueq(C). Crystal data, data collection, and structure
refinement of all compounds are presented in Table S1 (SI).
RESULTS AND DISCUSSION
■
Synthesis and Structures. The (trans-[bis(p-
methylthioetherbenzeneethynyl)bis(trimethylphosphine)-
platinum(II)), L1, was prepared by reacting 2 equiv of 4-
ethynylthioanisole with cis-dichlorobis(trimethylphosphine)-
platinum(II) in the presence of CuI and Et2NH as the base
(Scheme 1). Crystals suitable for X-ray analysis were obtained
in CH2Cl2 and reveal a trans-geometry about the Pt atom
(Figure 1, the X-ray data are in Table S1 of the SI). The
PtP2(CC)2 and C6H4 planes make an angle of 20.88°, and
the CCC−Pt−CCC axis is quasi linear.
Computation. The density functional theory (DFT) and time
dependent density functional theory (TD-DFT) calculations were
performed with Gaussian 0922 at the Universite
́
de Sherbrooke with
the Mammouth supercomputer supported by Le Reseau Quebecois De
́
́
́
Calculs Hautes Performances. All .cif files from X-ray crystal structures
have been used like optimized structures for calculations. The DFT
(singlet and triplet energy states) as well as TD-DFT calculations23−31
were carried out using the B3LYP method. VDZ (valence double ζ)
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Conversely, CuI reacts with L1 in PhCN to generate a 1D
material (CP2; Figure 3). The 1D chain is composed of (Cu2I2-
L1)n built upon (η2-CC)-Cu linkages and falls in the same
category of CPs stated above (see the CPs shown in Chart 1,
where the polynuclear copper unit is anchored onto the η2-
ethynyl function via the coordination of a -Cu2Br2-rhomboid10
or a -Ag2(O3SCF3)2-complex11).
In CP2, both metal atoms in the Cu2I2 rhomboid exhibit a
tetrahedral geometry where one PhCN solvent is bonded to
each copper (i.e., 1:1 solvent/Cu ratio). The high boiling point
of PhCN and the presence of the Cu−N coordination bond
would make the removal of the solvent more difficult (under
heat and vacuum). Again, L1 undergoes a distortion where a
C−CC angle of 156.8° and a smaller distance (compared to
L1 in CP1) between the two C6H4 planes of 0.973 Å are
measured. Noteworthy, the SMe groups are not involved in any
coordination interactions. Instead, Cu−N links are generated
and explain the formation of a 1D structure rather than the 2D
network observed for CP1. The flat structure of PhCN also
appears as a feature for its insertion between two L1 ligands
within the skeleton of the 1D polymer CP2.
Two 1D CPs are also formed, CP3 and CP4, when the salt is
CuCl regardless of the solvent and are of the same type as CP2
(Figure 4). The difference is that no Cu-solvent coordination
bonding is formed. Instead, the solvent is found as
crystallization molecules in their lattices. The C−CC bond
angles are 163.3° and 166.2° and dihedral angles of 44.7° and
24.5° are measured for the average planes between the SC6H4C
and trans-PtP2C2 units for CP3. Moreover, a dihedral angle of
58.6° is observed between the two C6H4 planes, thus
contrasting with the centrosymmetric L1 in CP1 and CP2.
Figure 1. ORTEP representation of L1. The thermal ellipsoids are set
at 50% probability. Yellow = S, purple = Pt, orange = P, blue = C,
white = H.
Ligand L1 reacts with CuX salts (X = Cl, Br, I) in PrCN and
PhCN to form 1D and 2D coordination polymers (CP, Scheme
1; the X-ray data are summarized in Table S1). The CuI salt
makes a 2D CP with L1 in PrCN (CP1) where the central
node is a Cu4I4 cluster exhibiting a step cubane geometry (i.e.,
two slipped Cu2I2 rhomboids fused in a staircase fashion, Figure
2). The Cu4I4 clusters exhibit two tricoordinated Cu atoms by
two I and one CC) and two tetracoordinated ones by two I,
one S, and one CC ligands. CP1 exhibits a mesh structure
through a series of (Cu4I4-L1)2 macrocycles formed by S-Cu4I4-
(η2-CC) coordination networks. The formation of these
macrocycles induces a distortion in the L1 skeleton where a C−
CC angle of 163.3° and a C6H4···C6H4 interplanar distance
of 1.688 Å are measured. An S-shape can be depicted for L1
inside the CP1 2D grid. Such distortion of the π-system is
suspected to influence the photophysical response of this
material in comparison with the uncoordinated ligand L1.
Inside these macrocycles, a PrCN crystallization molecule is
trapped. This solvent molecule is found to be disordered.
Figure 2. (a) ORTEP representation of a fragment of the 2D CP1. The thermal ellipsoids are set at 50% probability. Yellow = S, purple = Pt, brown
= Cu, orange = P, green = I, blue = C, white = H. Only one PrCN molecule is represented inside a cavity. (b) Local environment of L1 in CP1. (c)
View of the Cu4I4(η2-CC)2(S)2 unit. (d) Drawing of a segment of CP1. The X-ray data and some further description are in the SI.
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Figure 3. ORTEP representation of a fragment of CP2. The thermal ellipsoids are set at 50% probability. Yellow = S, pale purple = Pt, orange = P or
Cu when attached to two I, green = I, dark purple = N, blue = C, white = H.
Figure 4. ORTEP representation of a fragment of the 1D CP3 (left) and CP4 (right). The thermal ellipsoids are set at 50% probability. Yellow = S,
pale purple = Pt, orange = P or Cu when attached to two Cl, green = Cl, purple = N, blue = C, white = H.
The reaction between CuBr and L1 in PrCN or PhCN leads
to an isostrutural 2D network (Figure 5). However, the isolated
crystals from the two solvent mixtures only slightly differ from
the d(Cu···Cu), d(Cu−Br), d(Cu−S), and d(Br···Br) distances
(provided below), and they are called CP5 (PrCN) and CP5′
(PhCN) for convenience. The 2D grid is generated from
parallel placed 1D chains of (Cu2Br2-L1)n again built upon (η2-
CC)-Cu coordination bonds similar to that of CP3 and CP4
(Figure 4), interacting with the neighboring (Cu2Br2-L1)n
chains via two S−Cu linkages in an alternated fashion (i.e.: ···
Cu2Br2-L1*-Cu2Br2-L1-Cu2Br2-L1*-Cu2Br2-L1···, where L1*
and L1 are the ligands respectively involving and not involving
S−Cu linkages; Figure 5). Each ···Cu2Br2-L1*−Cu2Br2-L1···
chain is doubly linked via parallel Cu-(η2-CCC6H4S)2-Cu
rings where the C6H4 aromatics are placed face-to-face. This
coordination scheme generates large macrocycles (see cycles
made by the [red bar/green rectangle/red bar/green] units in
Figure 5) filled with two halves of L1 (i.e., the non-S-
coordinated ligand). This structural feature reveals the total
absence of voids, which otherwise could likely be accommodat-
ing crystallization solvent molecules. Again, this is not the case
here.
d(Br···Br) distances (Table 1) within the Cu2Br2S frame are
respectively 3.215, 2.496, 2.456, and 3.735 Å for CP5, and
3.225, 2.487, 2.459, and 3.727 Å for CP5′, showing only a
minor variation whether PrCN or PhCN is used as the
recrystallization solvent. The IR spectra were also monitored
for ν(CC). These values are 2108 cm−1 for L1 and ∼2106
cm−1 for CP1 to CP5′ (see Experimental Section for detail).
This very small decrease in ν(CC) also goes in the same
direction of the small CC bond lengthening (1.20 Å for L1,
to 1.23−1.25 Å for CP1 to CP5′; see Table S26 in the SI for
detail), suggesting the expected back bonding effect.
These six combinations of solvents and salts generate five
different CPs, indicating the high variability of outcomes upon
seemingly minor changes in the synthesis procedure and
making predictability very difficult. Table 2 compares various
structural features for these CPs trying to find correlations. The
(η2-CC)-Cu coordinations are clearly favored over Cu−S.
Statistically, the rhomboid dimer Cu2X2 is most often
encountered. This observation is fully consistent with the
general trends reported for 0D, 1D, 2D, and 3D CPs built upon
organic mono- and dithioether and CuX salts (X = Cl, Br, I).38
The most interesting trend is that when there is occurrence of
S−Cu bonding, the resulting CP exhibits a 2D dimensionality.
In these cases, large macrocycles are formed and can potentially
accommodate solvent crystallization molecules. This was only
the case for CP1. The following sections describe the physical
and photophysical properties of these CPs.
Similar S-shape distortions are also noted for L1 and L1* in
CP5 as mentioned for the other CPs (Figure 6). For instance,
the C−CC bond angles are 163.4° and 158.6° for L1 and
162.7° and 163.2° for L1*. Angles of 17.0° (L1) and 4.0°
(L1*) are also noted between the average C6H4 planes in L1
and L1*. The average d(Cu···Cu), d(Cu−Br), d(Cu−S), and
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Figure 5. ORTEP representation of a fragment of the 2D network of CP5 (which is isostructural to CP5′ except the Cu−Cu distances differ; the
detail is placed in Table 1). The thermal ellipsoids are set at 50% probability. Yellow = S, pale purple = Pt, orange = P or Cu when attached to two
Br, dark red = Br, blue = C, white = H. The red lines represent the Pt−Pt−Pt axes. The transparent yellow and green boxes respectively highlight the
non-S-coordinated and S-coordinated ligand L1.
Table 1. Bond Distances within the Cu2Br2S Rhomboids in
CP5 and CP5′
CP5 (rhomboid 1)
CP5 (rhomboid 2)
CP 5′
distances
(Å)
distances
(Å)
distances
(Å)
bonds
bonds
bonds
Cu2···
Cu1
3.222(3) Cu4···
3.207(3) Cu1···
3.2251(9)
Cu3
Cu2
Br1−Cu1
Br2−Cu1
Br1−Cu2
Br2−Cu2
Cu1−S3
2.464(3) Br3−Cu4 2.643(3) Cu1−Br1
2.659(3) Br4−Cu4 2.481(3) Cu1−Br2
2.416(3) Br4−Cu3 2.416(3) Cu2−Br2
2.410(3) Br4−Cu4 2.481(3) Cu2−Br1
2.6573(8)
2.4664(6)
2.4226(7)
2.4020(6)
2.4589(10)
2.445(6) Cu4−S4
2.466(6) Cu1−
S1#2
Br2···Br1
3.730(2) Br4···Br3
3.740(3) Br1···Br2
3.7270(1)
losses are recorded near 250 and 450 °C and are clearly
reminiscent of the thermal decomposition of L1.
Figure 6. ORTEP representation of the environment around L1. The
circle indicates the presence of S−Cu coordinations from L1 (labeled
L1* in the text).
Moreover, CP1 exhibits further decomposition past 500 °C,
which appears to be associated with the loss of I2. The key
feature in this series is that the PrCN molecule in CP1 is more
strongly retained inside the macrocycles than only being
surrounded by C6H4SMe and PMe3 groups within the 1D
structure of CP3. The fact that the weight loss of PrCN in CP3
resembles that of its boiling point (117−119 °C) corroborates
this feature. For CP2 and CP4, the situation is different, as
PhCN is less volatile (Tb = 188−191 °C; see SI for traces). In
fact, weight losses, starting at 95 °C, are observed, clearly
indicating the presence of decomposition, likely involving the
Thermal Gravimetric Analysis (TGA). The thermal
stabilities of CP1, CP3, CP5, and L1 (for comparison
purposes) were addressed using TGA (Figure 7). The loss of
PrCN in CP1 (∼4.6% weight loss) and CP3 (∼3.3%) occurs
respectively at ∼170 and ∼115 °C. No weight loss in these
regions is observed for CP5 and L1, which do not contain a
crystallization molecule in the lattice. The two next weight
F
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Table 2. Comparison of Selected Structural Features of CP1−CP5′
CP1
CP2
CP3
CP4
CP5
CP5′
cluster structure
Cu4I4
2D
Cu2I2
1D
Cu2Cl2
1D
Cu2Cl2
1D
Cu2Br2
2D
Cu2Br2
2D
CP dimensionality
crystallization mol.
PrCN
PrCN
PhCN
coordinated solvent
PhCN
(nb of trivalent Cu)/(nb of tetravalent Cu)
nb of Cu−S bonds
2/2
2
0/2
0
2/0
0
2/0
0
1/1
1
1/1
1
nb of Cu−X bonds
4
2
2
2
2
2
nb of Cu-(η2-CC) bonds
2
2
2
2
2
2
Figure 7. TGA traces (black) and 1st derivative of the TGA traces (gray).
a
solvent molecule. So, no reliable interpretation is possible in
these cases.
Gas Sorption Measurements. Gas sorption isotherms at
low-pressure ranging between 0 and 1100 mbar (∼1.1 atm)
were measured for CP1 (PrCN), CP3 (PrCN), and CP5 (no
solvent; Figure 8). The BET and DFT measurements reveal
Table 3. Gas Adsorption Data for CP1, CP3, and CP5
Quantity
Adsorbed
Surface
Area
Pore
T
P
Volume
Codes
Gas
[K] [mbar] (cm3/g STP)
(m2/g)
(cm3/g)
CP1
CO2
N2
273
77
1090
992
12.2
4.7
57.2
0.019
6.5
c
<0.01
c
CP3
CP5
CO2
N2
273
77
1046
991
5.7
1.5
3.7
<0.01
CO2
N2
273
77
1046
997
1.6
b
1.7
b
<0.01
b
a
For CO2, the estimation of the structural parameters was made using
by the DFT calculations model, while, for N2 gas, the surface area was
b
c
measured from BET. Too small to be measured. Not calculated.
are characterized by a maximum in the vicinity of 300−350 nm,
which compares favorably to that for L1 and in both solution
and the solid state (Figures S1 and S2). This latter signal is
assigned to spin-allowed ππ* mixed with ligand-to-metal
(LMCT), an assignment that is supported by DFT and
TDDFT computations below. Indeed, based on the computed
relative atomic contributions to the frontier MOs (DFT, Figure
S3 and Table S2) and the nature of the lowest energy electronic
transitions (TDDFT, Table S2) for L1, this intraligand ππ*/
LMCT assignment (L = MeSC6H4CC) is readily corrobo-
rated.
The graph reporting the computed oscillator strength, f, vs
the calculated position of the electronic transition generates a
bar plot. By assigning a thickness of 1000 cm−1 to each bar, a
spectrum is generated where the maximum matches approx-
imately that of the experimental spectrum (λ ∼ 300 nm, Figures
Figure 8. Left: CO2 sorption isotherms of CP1 (red), CP3 (black),
and CP5 (blue) measured at 273 K. Closed shapes = adsorption and
open shapes = desorption. Right: space filling model of CP1
illustrating the cavities available for gas sorption.
that the quantity of gas for N2 and CO2 (Table 3) being
adsorbed varies as CP1 > CP3 > CP5, which is consistent with
the fact that CP5 exhibits minimal voids and that CP1 exhibits
large macrocycles in the lattice (Figure 8).
Absorption and Emission Properties. The solid state
absorption (from reflectance), excitation, and emission spectra
of L1 and CP1-−P5 at 298 K are shown in Figure 9 (see
Figures S1 and S2 for the 77 K data). The absorption spectra
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Figure 9. Solid state absorption (black), excitation (blue), and emission (red) spectra of L1 and CP1−CP5 at 298 K. The chromaticity diagrams and
data are placed in the SI.
9 and S4). This computational observation is consistent with
previous findings reported by Cooper and collaborators where a
mixing is also computed for the trans-C6H5CCPt(PR3)2C
CC6H5 related complexes.39 In this case, the authors mentioned
the presence of the ππ*-type of electronic transitions mixed
with both LMCT and metal-to-ligand charge transfer (MLCT)
where M = Pt (dxy).
For CP1−CP5, again the absorption spectra exhibit the same
features as for L1 and they were also addressed using DFT and
TDDFT (Figures 10 and S5, Tables 4 and S5). CP1 is only
discussed here, but the conclusions are consistent with those
for CP2−CP5, except that CP2 shows some differences
presented below. Selected MO representations of CP1 exhibit
two distinct types of atomic contributions (Figure 10). The first
type consists of atomic contributions concentrated on L1 for
both filled and empty MOs, whereas for the second type, the
contributions are localized on the Cu4I4 motif mainly for some
filled MOs. Such a situation leads to two possible combinations
of excited states: intra-L1 (mainly ππ*/LMCT discussed
above) and metal-to-ligand charge transfer (Cu4I4 → L1).
TDDFT computes the positions of the first spin-allowed
electronic transitions, λ, and their oscillator strengths, f (Table
5).
The emission spectra of CP1 exhibit vibronic structures that
are reminiscent of that of L1 at 298 (Figure 9) and 77 K
(Figure S2), but they also exhibit a broad featureless band
centered near 560 nm. More importantly, to ensure that the
nature of the analyzed bulk solid samples is the same as the
crystal structure, in all cases crystals were selectively chosen
under the microscope and ground so that the samples fit inside
capillaries. These emissions are found to arise from the triplet
states because of the large Stoke shift (∼9800 cm−1) between
the absorption maximum (325 nm) and the emission peak (476
nm for L1, for instance), and because of the microsecond time
scale for the emission lifetimes (Table 6). Moreover, the
absorption spectra for L1, CP1, and CP3 exhibit an absorption
signal going from the maximum peak all the way down to the
occurrence of the emission supporting the triplet assignment
(i.e., these long tails contain S0 → Tn processes visible, as the
Beer−Lambert law no longer applies in the solid state).
Biexponential decays are observed in most cases, except for
CP5 (CP5′), for which triple exponentials are observed at best
fits. This biphasic behavior is inherent to L1 itself, as it is also
observed for the ligand L1 in solution at 77 K (Figure S1). The
origin of this phenomenon is still unknown but is found
reproducible for all CPs. The nature of this excited state was
addressed by DFT. The representations of the semioccupied
frontier MOs for CP1 in its lowest energy triplet state (Figure
12) indicate that the nature of this state is intraligand mainly.
The relative atomic contributions corroborate this observation
(Table 7), including those for both LSOMO-1 and HSOMO+1
(i.e., ∼85 2% are located within the π-system of L1).
The calculated positions for the transitions with f ≠ 0 (at 347
and 351 nm) fall just near the maximum observed in the
experimental spectrum (Figure 9). Indeed, a constructed
spectrum built upon a bar graph (again f vs λ; Figure 11)
shows a large concentration of transitions between 300 and 350
nm. The computational conclusion is that the lowest energy
singlet excited states are mainly ππ* with some minor MLCT
(Cu4I4 → L1) contributions.
The conclusion drawn for the lowest-energy triplet state is
also true for the other CPs (see SI). The discussion will not be
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Figure 10. MO representations of the frontier MOs for CP1 (see SI for CP2−CP5).
a
Table 4. Relative Atomic Contributions (%) of the Various Fragments to the Frontier MOs of CP1
Fragments
H−4
H−3
H−2
H−1
HOMO
LUMO
L+1
L+2
L+3
L+4
L1
50.1
27.1
22.8
78.8
14.7
6.5
68.2
19.4
12.4
67.5
20.1
12.4
61.7
25.7
12.6
85.1
10.4
4.5
88.9
7.0
88.8
7.2
87.2
8.5
84.2
14.6
1.2
Cu atoms
I atoms
4.1
4.0
4.2
a
H = HOMO, L = LUMO; the values in bold represent contributions >50%.
Table 5. Calculated Position of the First 8 Electronic Transitions, Oscillator Strengths (f), and Their Major Contributions (H =
HOMO, L = LUMO; see Table S5 for the first 100 transitions)
λ (nm)
f
Major contributions (%)
353.0
351.4
347.2
346.5
343.9
340.3
338.4
337.2
0
H-1→LUMO (17), HOMO→L+1 (41), HOMO→L+3 (10)
HOMO→LUMO (45), HOMO→L+2 (11)
H-3→LUMO (10), H-2→L+1 (25), H-2→L+3 (14), HOMO→L+2 (18)
H-3→L+1 (11), H-2→LUMO (24), H-2→L+2 (15), HOMO→L+3 (17)
H-4→LUMO (13), H-1→LUMO (46)
0.8786
0.8553
0
0
0.1262
0
H-1→L+1 (58)
H-1→L+2 (48), HOMO→L+3 (11)
0.17
H-1→L+1 (10), H-1→L+3 (48)
repeated here, but a focus is now provided for the differences
noted for CP2 and between CP5 and CP5′.
+1, LUMO+2, and LUMO+3) that exhibit such type of atomic
contributions show only contributions of this ligand and not or
almost not from L1 and the Cu2Br2 rhomboid (Table S6).
Conversely, for the highest energy filled MOs (HOMO,
HOMO+1, HOMO+2), the atomic contributions are mostly
located on L1 and the Cu2Br2 rhomboid. The computed lowest
For CP2, the representations of the frontier MOs indicate
the presence of atomic contributions from the coordinated
benzonitrile ligands for some MOs (Figure S6). The
particularity is that the lowest energy MOs (LUMO, LUMO
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Figure 12. Representations of the semioccupied MOs for CP1 in its
lowest energy triplet state.
Table 7. Relative Atomic Contributions (%) of the Various
Fragments to the Semi-occupied MOs of CP1 in Its Lowest
Energy Triplet Excited States
Figure 11. Bar graph reporting the computed oscillator strengths and
their positions for the 80st electronic transitions of CP1. The black
line is generated by assigning a thickness of 1000 cm−1 to each bar. (H
= HOMO, L = LUMO.)
a
LS-1
LSOMO
HSOMO
HS+1
L1
85.3
10.9
3.8
84.6
11.5
4.0
86.9
7.4
82.8
11.1
6.1
energy electronic transitions are charge transfer processes L1/
Cu2Br2 → benzonitrile. Because there is an obvious lack of MO
coupling between the L1/Cu2Br2 and benzonitrile units (as the
atomic contributions are mostly placed on one side and not the
other), the computed f values for these electronic transitions
are bound to be small, as computed. Their positions are located
at wavelengths exceeding ∼360 nm. The most intense
transitions are placed between 300 and 350 nm (Figure S7),
which are consistent with the experimental absorption
spectrum (Figure 9). Similarly, the representations of the
semioccupied MOs in the triplet states exhibit atomic
contributions in L1 almost exclusively in the LSOMO and
LSOMO-1) and mainly in the benzonitrile unit for the
HSOMO and HSOMO+1 (Table S7). The emissive triplet
Cu atoms
I atoms
5.7
a
The fragments exhibiting the largest contributions are placed in bold
to allow an easy identification (LS = LSOMO, HS = HSOMO).
contributions to the MOs and semioccupied MOs (Tables
S15, S17, S18, and S20), computed positions and oscillator
strengths of the electronic transitions (Table S16 and S19), and
calculated spectra (Figures S13 and S14). The conclusion
drawn from these computations is that the spin-allowed
electronic transitions may extend all the way down to 400
nm, which is even more red-shifted compared to CP1−4, and
they corroborate the experimental spectra (Figures 9 and S2),
are of the same nature as for CP1, CP2, and CP4 (i.e., the
lowest energy singlet excited states are mainly ππ* with some
minor MLCT (Cu4I4 → L1) contributions). Interestingly, the
calculated positions of the lowest energy spin-allowed
electronic transitions are 401 and 383 nm for CP5 and CP5′,
respectively, and the observed positions of the emission maxima
are 606 and 590 nm at 298 K, and 576 and 570 nm at 77 K,
respectively. This corroboration brings support for the
assignment of the nature of the emissive states. The complexity
of the emission decays is specific to CP5 and CP5′ (which is
the same polymers), and the DFT computations did not bring
any possible explanation for this phenomenon. Speculatively,
one may suspect that the emissive sites at the surface of the
microcrystals are different from those inside them and so the
3
excited state is (L1→ benzonitrile)*, and experimentally the
position is somewhat red-shifted, which is consistent with the
red-shifted calculated positions of the electronic transitions
(TDDFT). The spectral signature (Figures 9 and S2) bears a
resemblance to that of CP1 (some vibronic features are
present), and the emission lifetimes (τe) exhibit biphasic
behavior (inherent to the presence of L1) as well, and are
found to be of the same order of magnitude as those for CP1.
For CP5 and CP5′, their formulas are identical but the use of
different solvents (PrCN and PhCN) leads to two slightly
different structures where in the former one two slightly
different rhomboids are depicted. This difference leads to small
differences in MO and semioccupied MOs representations
(Figures S15, S17, S18, and S20), calculated atomic
a
Table 6. Lifetime Measurements for CP1, CP2, CP3, CP4, CP5, and CP5′ at 298 and 77 K in the Solid State
2
λem (nm) 298 K
Bi
τe (μs) 298 K
χ2
Φe (%) 298 K
λem(nm) 77K
Bi
τe (μs) 77 K
χ
L1
476
0.0761
0.0091
0.0569
0.0208
0.1013
0.0121
0.0020
0.0196
0.0219
0.0105
0.0732
0.0518
0.0041
0.0231
0.0139
1.11
3.14
2.08
7.45
1.08
7.64
2.01
14.9
2.29
12.6
0.06
1.32
9.48
1.34
10.3
1.042
20
511
0.0134
0.0538
0.0232
0.0166
0.0527
0.0306
0.0145
0.0222
0.0442
0.0388
0.0554
0.0173
0.0053
0.015
10.8
50.7
21.0
39.7
8.98
30.4
15.7
31.3
15.7
33.4
1.68
8.96
28.3
1.99
12.0
30.7
1.023
1.012
1.021
1.064
1.019
1.046
CP1
CP2
CP3
CP4
CP5
568
580
592
605
586
1.043
1.042
1.055
1.022
1.081
15
12
25
18
16
555
577
590
575
571
CP5′
603
1.039
15
575
1.027
0.023
0.018
a
The uncertainty on τe is ∼ 5%; Bi = pre-exponential factor.
J
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Figure 13. Emission spectra of CP1 (red), after solvent removal (black), after reintroduction of a solvent vapor: MeOH (green) and MeCN (blue)
at 298 (left) and 77K (right).
deactivation kinetics (relative quantum yields and lifetimes)
differ. Furthermore, the occasionally observed vibronic features
placed on the high energy side of the central broad emission
band may also reflect a surface effect where some η2-(CC)Cu
bonds are present for some sites and not for others (i.e.,
partially uncoordinated L1s). This particular feature is hard to
confirm unless one performs a systematic grounding effect of
the microcrystals on their photophysical properties under
investigated, which is not the purpose of this investigation.
The key information provided by this photophysical study is
that L1 is emissive at 298 K, both in the solid state and in
solution, as well as its corresponding CPs. The motif C6H5C
the chromaticity diagram but not exactly. This behavior arises
from a modification of the low-intensity vibronic shoulders
placed on the high-energy side of the emission band. This
behavior may reflect that the environment of the emissive sites
giving the resolved emission signal on the blue side of the
spectra is not rigorously identical upon exchanging the solvent
molecules. This observation is consistent with the speculation
stated above where the resolved signal is associated with L1
missing one η2-(CC)Cu bond at the surface. So, upon
reintroduction of the smaller vapor molecules, obviously,
diffusing through the surface prior to entering the core of the
microcrystals would modify the surface environment (i.e.,
solvent molecules are placed close to the uncoordinated η2-
(CC) site). No major difference in emission lifetimes is
noted when exposing CP1 to various solvent conditions (Table
S23 in the SI). L1, CP3, and CP5 show no drastic difference in
both emission spectra and chromaticity data upon solvent
exposure (see SI (Figures S26, S27, and Table S25) for CP3
and CP5).
40
CPt(PR3)2CCC6H5 ([Pt]) and its ([Pt]-G)n CPs (G =
Cu2Br2; Ag2(CF3SO3)2)10,11 are not emissive at 298 K.
Similarly, this motif is also nonemissive in some organic
conjugated polymers ([Pt]-G)n (G = -N = C6X4 = N-, X =
OMe, OEt, H, F, Cl).41 Conversely in rare cases, upon
substitution of the [Pt] synthon (with PBu3) by n-C3H7 (λfluo
=
374 nm; ΦF = 3.8%) and NO2 (λfluo = 468 nm; ΦF = 1.6%) at
the para-positions, some species are found to be fluorescent at
room temperature with 1.29 < τF < 1.47 ns, as well as
phosphorescent (NO2; λphospho = 587 nm; τP = 5.2 μs).42 The
situation is similar for L1 (λfluo = 370 nm but τF < 0.09 ns; SI),
but again two τP values are extracted. Interestingly, the
corresponding CPs are also found to be emissive and the
following study concerns the effect of removing the
crystallization molecules on their photophysical parameters.
Vapochromism of CP1. CP1 is the material that exhibits
the most gas sorption properties (Figure 8, Table 3). The
emission behavior was studied upon removing the crystal-
lization molecules with heating under reduced pressure of 600
mbar at 110 °C and then upon exposing the material to vapor
of acetonitrile (MeCN) and methanol (MeOH) in a desiccator
for 2 days (Figure 13, Figure S23 and Table S22).
Upon removing the solvent (PrCN), a clear red-shift of ∼20
nm (from 568 to 583 nm) is depicted in the emission spectra of
CP1 at 298 and 77 K (see red and black traces in Figure 13).
Such photophysical behavior is common. For example, this
phenomenon was also reported by Cho and his collaborators,
who observed a red-shift of the emission band upon heating the
samples.43 This small ∼20 nm shift in CP1 is accompanied by
an expected small change in chromaticity data (see red and
turquoise points in Figure S23). Upon exposing the material to
MeCN and MeOH vapor, the emission band now blue-shifted
back to the same position as for CP1 (which contains a PrCN
crystallization molecule) again at 298 and 77 K. This behavior
indicates that the new solvent molecules most likely occupy the
vacant positions of the previously placed PrCNs. The
chromaticity data also return close to the original position in
CONCLUSION
■
The luminescent metal-containing ligand L1 exhibits two
coordination sites, -S- and -(CC)-. The latter function
systematically favors the coordination of Cu(I). No reliable
trend was noted for the resulting cluster geometry (mainly the
Cu2X2 rhomboid, 4 examples out of 5) and the dimensionality
of the CPs (two 2D and three 3D) regardless of the solvent and
halide used. However, two examples form 2D CPs and involve
S−Cu coordination bonding. The resulting photophysical
spectra and data for the CPs turned out to be complex,
where the emission decays are biexponential, characteristic of
L1 itself, and the spectra can exhibit some vibrational
structures, reminiscent of that observed for the uncoordinated
L1, accompanied by a broad red-shifted signal. These latter
features may be due to L1 located at the surface of and inside
the microcrystals. The more porous CP1 was also examined
when the macrocycles of the 2D mesh structure are empty or
filled with various solvent molecules incorporated by exposition
to vapor. Only a modest shift (of ∼20 nm) in emission
maximum is noted between the empty (red-shifted) and filled
cavity (blue-shifted), meaning that this CP cannot be used as an
efficient sensor for vapor. Similar comments can be specified
when examining the emission lifetime and chromaticity data.
The small variation observed in the band maxima and
chromaticity data (with the empty cavity being slightly different
from the filled one) can be associated with ring stress caused by
the molecule insertion and release. Future design of 2D and 3D
(and MOF) materials would obviously rely on the presence of
an anchoring site onto the chromophore metal-containing
K
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Inorganic Chemistry
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has never been exploited for this purpose but is clearly a good
candidate based on the current data.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.6b01703.
■
S
Summary of X-ray data collection and refinement of L1
and CP1−CP5′, photophysical properties of L1 (in
solution) and of L1 and CP1−CP5′ in solid state at 77
K, electronic transition energy, oscillator strength (f),
major contributions of the first 100 and 80 singlet−
singlet electronic transitions TDDFT-calculated for L1
and CP1−CP5′, respectively, representative MOs and
relative atomic distributions of DFT-calculated frontier
MOs for L1 and CP2−CP5′, chromaticity of L1 and
CP1−CP5′ at 298 and 77 K. Crystallographic data in
CIF format of all compounds are also provided. (PDF)
Crystallographic data in CIF format for L1 (CIF)
Crystallographic data in CIF format for CP1 (CIF)
Crystallographic data in CIF format for CP2 (CIF)
Crystallographic data in CIF format for CP3(CIF)
Crystallographic data in CIF format for CP4 (CIF)
Crystallographic data in CIF format for CP5 (CIF)
Crystallographic data in CIF format for CP5′ (CIF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail: Pierre.Harvey@USherbrooke.ca.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The work was supported by the Natural Sciences and
Engineering Research Council of Canada (NSERC), the
Fonds de recherche du Quebec-Nature et technologies
́
(FRQNT), and the Centre Quebecois des Materiaux
Fonctionnels (CQMF).
■
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