A "flexible" Rigid Rod, trans-Pt(PMe3)2(C-CC6H4CN)2 (L1), to Form 2D [{Cu2(μ2-X)2}2(μ4-L1)]n Polymers (X = Br, I) Exhibiting the Large

Article abstract of DOI:10.1021/acs.inorgchem.8b00899

The trans-Pt(PMe₃)₂(C-CC₆H₄CN)₂ organometallic ligand L1, which is prepared from 4-ethynylbenzonitrile and cis-Pt(PMe₃)₂Cl₂, binds CuX salts to form two strongly lumin

Full text of DOI:10.1021/acs.inorgchem.8b00899

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
A “Flexible” Rigid Rod, trans-Pt(PMe ) (CCC H CN) (L1), to Form
3
2
6 4
2
2
D [{Cu (μ ‑X) } (μ ‑L1)] Polymers (X = Br, I) Exhibiting the Largest
2 2 2 2 4
Bathochromic Emissions
n
Frank Juvenal, Daniel Fortin, and Pierre D. Harvey*
́ ́ ́
Departement de Chimie, Universite de Sherbrooke, Sherbrooke, Quebec J1K 2R1, Canada
*
S Supporting Information
ABSTRACT: The trans-Pt(PMe ) (CCC H CN) organometallic
3
2
6
4
2
ligand L1, which is prepared from 4-ethynylbenzonitrile and cis-
Pt(PMe ) Cl , binds CuX salts to form two strongly luminescent two-
3
2
2
dimensional coordination polymers (CPs) [{Cu (μ -X) } (μ -L1)] (X =
2
2
2
2
4
n
I, CP1; X = Br, CP2). The emission quantum yields, Φ ≈ 30% at 298 K,
e
are the largest ones for all CPs built upon the trans-Pt(PMe ) (C
3
2
CC H X) motifs (X = SMe, CN). X-ray crystallography reveals that, to
6
4
2
accommodate these layered CPs, L1 must undergo major distortions of
the CC−C angles (∼159°) and significant rotations about the Pt-CC
bonds, so that the dihedral angles made by the two aromatic planes is 90°
in a quasi-identical manner for both CPs. Together, these two features
represent the largest distortion for trans-Pt(PMe ) (CCC H X) complexes among all of the CPs built upon this type of
3
2
6
4
2
ligand (2 of 16 entries). Concurrently, CP1 and CP2 also exhibit the most red-shifted emissions (λ = 650 and 640 nm,
max
respectively) known for this type of chromophore at room temperature. The {Cu (μ -X) } rhomboids adopt the trans- (X = I,
2
2
2
common) and cis-geometries (X = Br, extremely rare) making them “isomers” if excluding the fact that the halides are different.
Density functional theory (DFT) and time-dependent DFT suggest that the triplet emissive excited state is metal/halide-to-
ligand charge transfer in both cases despite this difference in rhomboid geometry.
INTRODUCTION
defined as a mixed excited state including intraligand-L2 (ππ*/
ligand-to-metal charge transfer (LMCT; i.e., C H CC →
Pt)) and metal-to-ligand charge transfer (MLCT; M = Cu X
2 2
■
1
6
4
The use of organometallic ligands for the formation of
2
bimetallic coordination polymers (CPs), metal-organometallic
3
or Cu I ; L = L2). Their emission bands exhibit maxima
4 4
framework (MOMF), and two-dimensional (2D) nanoparticle
4
ranging from 570 to 605 nm, which are significantly red-shifted
in comparison with that for L2 when not coordinated (476 and
vibronic peak at 511 nm). When X = Br and Cl, only rhomboid
SBUs are formed along with mainly 1D CPs (but not
exclusively). Several questions remain; (1) can 2D CPs be
obtained when using a N-donor linkers, (2) why some 2D CPs
exhibit cavities available for crystallization molecules, while
others do not have sufficient space to create solvent sites, and
finally (3) is there a structure−property relationship that
explains why these emissions are so red-shifted compared to the
uncoordinated ligands?
network has been the topic of recent interest for applications
in gas storage and sensors, catalysis, and optoelectronics.
Difunctionalized ferrocenyls and metallocenes are classic
fragments for the design of such heterobimetallic materials.
5
Conversely, the so-called “rigid rod” and generally luminescent
trans-Pt(PR ) (CCAr) synthon ([Pt], R = alkyl, Ar =
3
2
2
aromatic) is well-known for the design of one-dimensional
(
1D) organometallic polymers with applications in liquid
6
crystals, nonlinear optics (including up conversion, two-
7
photon absorption, and optical power limiting), light-emitting
8
9
diodes, and solar cells. Recently, our group reported the use
of a novel [Pt]-containing organometallic ligand, trans-
Pt(PMe ) (CCC H SMe) (see L2 in Chart 1), which
We now report the synthesis and characterization of CP1
and CP2 exhibiting formula [{Cu (μ-X) } (μ -L1)] , which
2
2
2
4
n
3
2
6
4
2
2
answer these questions. During the course of this investigation,
two new features are discovered. First, the emission maxima are
exhibits two coordination sites (η -CC and S), for the
formation of luminescent 1D and 2D CPs with CuX salts (X =
1
0
the most red-shifted ones in the [Pt]-containing CPs (λmax
50 nm and extending well above 800 nm), and second, the
Cu X SBUs present both the trans- (X = I) and cis- (X = Br)
=
Cl, Br, I). The common features are first, when Cu−S
linkages are used in the coordination network, a 2D CP is
systematically generated. This observation is entirely consistent
6
2
2
2
b,c
geometries, making CP1 and CP2 “isomeric” materials. The
that only 1D CPs are obtained with L0 (Chart 1). Second,
the coordination of either the resulting rhomboid Cu X (X =
11
latter form is rare and relies on bridging ligands.
2
2
Cl, Br, I) or staircase Cu I secondary building units (SBUs)
induce sensitive distortions of the [Pt] skeleton, and the
4
4
Received: April 3, 2018
formation of a charge transfer emissive triplet excited state
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b00899
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Chart 1. Structures of the [Pt]-Containing Organometallic Ligands and CPs
EXPERIMENTAL SECTION
The steady-state fluorescence spectra were recorded using capillary.
These spectra were corrected for instrument response. Phosphor-
escence lifetime measurements were made with an Edinburgh
instruments FLS980 phosphorimeter equipped with “flash” pulsed
lamp. The repetition rate 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, which is equipped with an integration sphere
that allows the direct measurements of emission quantum yields. The
thermogravimetric analysis (TGA) traces were acquired on a
PerkinElmer TGA 7 apparatus in the temperature range between 20
and 850 °C at 10 °C/min under argon atmosphere. All the figures
were treated using the Origin software.
X-ray Crystallography. A clear intense yellow prismlike single
crystal of CP1 was measured on a Bruker Kappa APEX II DUO CCD
system equipped with a TRIUMPH curved crystal monochromator
and a Mo fine-focus tube (λ = 0.710 73 Å). A clear pale yellow
prismlike single crystal of L1 and clear intense yellow platelike single
crystal of CP2 were measured on a Bruker Apex DUO system
equipped with a Cu Kα ImuS microfocus source with MX optics (λ =
■
Materials. 4-Bromobenzonitrile, trimethylsilylacetylene, triethyl-
amine, and tetrahydrofuran (THF) were purchased from Sigma-
Aldrich and were used as received without further purification except
THF, which was distilled before use.
-Ethynylbenzonitrile. 4-Bromobenzonitrile (5.214 g, 28.6 mmol),
trimethysilylacetenene (5.8 mL, 40.8 mmol), THF (35 mL),
4
triethylamine (35 mL), PdCl (PPh ) (0.330. g, 0.470 mmol), and
2
3 2
CuI (0.054 g, 0.284 mmol) were placed in a round-bottom flask, and
the mixture was stirred under argon at 50 °C for 24 h. The reaction
mixture was cooled at room temperature, and the solvent was removed
on the rotovap. Purification was done by column chromatography on
silica gel (CHCl /hexane: 1:7, v/v). Yield: 96%. The deprotection of
3
the product was done using K CO (10.60 g, 78.0 mmol) in MeOH/
2
3
THF (45 mL/45 mL) and stirring the mixture overnight. The solution
was filtrated, and the solvent was removed on the rotovap. The final
solid product was further dried under a vacuum. Yield: 69%. H NMR
1
(
2
300 MHz, CDCl ) δ 7.62 (d, J = 8.6 Hz, 2H), 7.57 (d, J = 8.6 Hz,
3
H), 3.30 (s, 1H).
Synthesis of the trans-Bis(4-ethynylbenzonitrile)bis-
trimethylphosphine)platinum(II) ligand (L1). 4-cis-Dichlorobis-
trimethylphosphine)platinum(II) (0.81 g, 1.9 mmol) and ethynyl-
benzonitrile (0.62 g, 0.4.9 mmol) were added in a degassed solution of
Et NH (90 mL) placed in round-bottom flask, and CuI (6 mg, 0.03
mmol) was added to the mixture. The reaction mixture was stirred at
(
(
1
.541 78 Å). Diffraction data were recorded at 173 K for L1, CP1, and
CP2. The integration of the data using triclinic, monoclinic, and
orthorhombic unit cell yielded total reflections of 3453, 7200, and
32 279 for L1, CP1, and CP2, respectively. The frames were integrated
2
12
with the Bruker SAINT Software package using a narrow-frame
5
0 °C for 24 h. The solid was washed with cold water and cold
algorithm for CP1 and used wide-frame algorithm for L1 and CP2.
1
methanol. Yield: 76%. H NMR (300 MHz, CDCl ) δ 7.49 (d, J = 8.3
3
Data were corrected for absorption effects using the multiscan method
31
Hz, 4H), 7.34 (d, J = 8.3 Hz, 4H), 1.83−1.67 (m, 18H). P NMR
12
(
SADABS). The structures were solved and refined using the Bruker
(
122 MHz, CD Cl ): δ −20.51 (s, J = 2493 Hz). Anal. Calcd for
2
2
Pt−P
SHELXTL Software Package using space group P1, with Z = 1 for L1,
space group P121/m1 with Z = 2 for CP1 and space group Pnma, with
Z = 4 for CP2. All non-hydrogen atoms were refined with anisotropic
thermal parameters. The hydrogen atoms were placed in calculated
positions and included in final refinement in a riding model with
isotropic temperature parameters set to U (H) = 1.5 U (C). Crystal
C H N P Pt (599.5): C, 48.03; H, 4.34; N, 4.67%. Found: C, 47.83;
2
4
26
2 2
−1
H, 4.35; N, 4.45%. IR (cm ): 2959, ν(CH); 2883, ν(CH); 2215,
ν(CN); 2109, ν(CC).
Synthesis of the CPs. The CPs were synthesized by solvothermal
method, whereby L1 was placed in a vial with degassed MeCN under
argon. CuX (X = I, Br) was added, and the resulting mixture was
stirred for 2 h and heated for 4 h at 80 °C. The solution was slowly
cooled to room temperature, and yellow crystals appeared. These were
collected and analyzed by single-crystal X-ray diffraction.
iso
eq
data, data collection, and structure refinement of all compounds are
provided in Table S1. The X-ray data for CP2 were of lower quality,
despite multiple attempts, due in part to the small size of the crystals
available. Both Cu and Mo X-ray sources were also used. When the
Mo source was employed, many reflections were overlapping making
their integration unreliable. Concurrently, the best data were obtained
with the Cu source (R1 = 0.0925).
Powder X-ray Diffraction. L1, CP1, and CP2 were measured at 173
K on a Bruker APEX DUO X-ray diffractometer. Six correlated runs
per sample with Phi Scan of 360° and exposure times of 270 s were
collected with the Cu microfocus anode (1.541 84 Å) and the CCD
APEX II detector at 150 mm distance. These runs, from −12 to −72°
2θ and from 6 to 36° ω, were then treated and integrated with the
XRW2 Eval Bruker software to produce WAXD diffraction patterns
from 2.5 to 82° 2θ. The patterns were treated with Diffrac.Eva version
2.0 from Bruker.
Synthesis of CP1, [(Cu I ) (L1)] . L1 (30.0 mg, 0.05 mmol), CuI
2
2 2
n
(
19.0 mg, 0.1 mmol), and 5 mL of MeCN. Yield: 63%. Anal. Calcd for
C H Cu I N P Pt (980.38): C, 29.37; H,2.65; N, 2.86%. Found: C,
2
4
26
2 2
2 2
−
1
2
2
9.40; H, 2.70; N, 3.20%. IR (cm ): 2976, ν(CH); 2898, ν(CH);
231, ν(CN); 1981, ν(CC).
Synthesis of CP2, [(Cu Br ) (L1)] . L1 (30.0 mg, 0.05 mmol), CuBr
2
2 2
n
(
14.0 mg, 0.1 mmol), and 5 mL of MeCN. Yield: 63%. Anal. Calcd for
C H Br Cu N P Pt (886.4): C, 32.49; H, 2.93; N, 3.16%. Found: C,
2
4
26
2
2
2 2
−1
3
2
3.08; H, 3.21; N, 3.37%. IR (cm ): 2974, ν(CH); 2913, ν(CH);
230, ν(CN); 1977, ν(CC).
Instruments. The H and 13P nuclear magnetic resonance (NMR)
1
spectra were recorded on a Bruker Avance 300 Ultrashield NMR
spectrometer using CDCl and CH Cl as solvents. Elemental analyses
Computations. The calculations done included the density
3
2
2
were performed on a TruSpec Micro Series for C, H, and N. The
infrared (IR) spectra were measured using ABB Bomem, MB series
FT-IR spectrometer. Solid-state UV−vis spectra were recorded using
Varian Cary 50 spectrophotometer at 298 and 77 K with raised-angle
transmittance apparatus having homemade 77 K sample holder.
Steady-state fluorescence and excitation spectra were measured on
Edinburgh instruments FLS980 phosphorimeter, which is equipped
with single monochromators. All samples were crushed prior to use.
functional theory (DFT) and time-dependent density functional
13
theory (TD-DFT) and were performed with Gaussian 09 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 (L1, CP1, CP2) were used for
the calculations, except for L1 in solution (for comparison purposes),
for which the geometry was optimized. The DFT (singlet and triplet
1
4−23
energy states) and TD-DFT calculations
were performed using
B
DOI: 10.1021/acs.inorgchem.8b00899
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
the B3LYP method. The 6-31g* basis set was used for C, H, N, and P
and the dihedral angles made by the C H aromatic planes (see
Table 1 (three entries: L1, CP1, and CP2) and the comparative
6
4
2
3
atoms. Valence double ζ (VDZ) with SBKJC effective core
2
4−29
potentials were used for all Cu, I, Br, and Pt atoms.
3T0he
Table S3 containing all related CPs (16 entries for CPs and 4
calculated absorption spectra were obtained from GaussSum 3.0.
2,10,32
entries for their corresponding metal−ligands)).
These
tables compare the interplanar C H ···C H distances, C−C
6
4
6
4
RESULTS AND DISCUSSION
■
C angles, and dihedral angles formed by C H planes and the
6 4
Synthesis and Characterization. CP1 and CP2 were
prepared by solvothermal reaction using CuX salts (X = I, Br)
and L1 in acetonitrile (Scheme 1).
PtP C one of related zero-dimensional (0D) complexes and
2 2
1D and 2D CPs. The most remarkable feature is the dihedral
angles formed by the two C H aromatics (90°), which is by far
6
4
the largest in this series (i.e., 16 CPs and 4 complexes). The
only exception is the one for the 1D CP of formula [(Cu Cl )
a
Scheme 1. Synthesis of L1, CP1, and CP2 in MeCN
2
2
10b
L2·PhCN]n,
Similarly, C−CC angles averaging 159.7° (CP1) and
58.4° (CP2) are the fourth smallest one when averaging all
angles. The three other examples that exhibit C−CC angles
which exhibits a similar angle of 86.77°.
1
1
0a
less than 158.4° are 1D [(Cu Br )L3] (155.0°),
1D
2
2
n
10a
[
(Cu Cl )L3] (155.3°) (L3 = MeSC H CC−Pt(PEt ) -
2
2
n
6
4
3 2
0b
1
CCC H SMe), and 1D [(Cu I )(PhCN)L2] (156.9°).
6
4
2 2
n
Conversely, these last examples show no distortion in the
C H ···C H dihedral angle (i.e., 0°). In conclusion, L1 appears
6
4
6
4
the most distorted [Pt]-ligand.
The CuX salts (X = Cl, Br, I) are known form various SBUs
during the formation of CPs, including the frequently
encountered Cu I L step cubane, Cu I L cubane, Cu I L
a
(
i) cis-PtCl (PMe ) , NHEt , CuI. (ii) CuX.
4 4
6
4 4
4
4 4 6
2
3
2
2
open cubane, and Cu I L hexagonal prism (L = N-, S-, O-, η -
6
6
6
2
CC). However, the rhomboid Cu X L (X = Cl, Br, I) is by
2
2 4
far the most common motif encountered indicating that this
geometry appears to be the most accommodating, presumably
The identity of L1 was confirmed by X-ray crystallography
1
31
(
Figure S1), H and P NMR (Figures S2−S4), and IR
spectroscopy (Figure S5 and Table S2), whereas that for CP1
and CP2 was demonstrated by X-ray structure determination
33
because of its small size. Concurrently, this list of possible
geometries for SBUs is also far from being exhaustive (Cu I L
8 8
6
3
4
33
fused dicubane, (CuXL) staircase polymer, Cu Br L
(
Figure 1) and IR (Figure S5 and Table S2).The trans-
n
5
5
6
35
capped square, among many others), hence demonstrating
the rather high flexibility of these (CuX) clusters. In this work,
a mixed-ligand environment is present (L = CN, L′ = η -C
C), and unsurprisingly rhomboid Cu L′ SBUs are
observed. Interestingly both geometries, trans- (CP1) and cis-
(CP2) were isolated. Many precedents of the trans-Cu L′
motifs exist (X = Cl, Br, or I; L and L′ = (N-donor/η -C
geometry of L1 was also confirmed by the value of the coupling
31
constant JPt−P = 2493 Hz.
n
2
The X-ray data for L1 reveal that the CCC−Pt−CCC
axis is quasilinear (average ∠C−CC ≈ 175.1° and ∠Pt−C
2
X
2
L
2
2
−1
C ≈ 176.5°). The ν(CC) (2109 cm for L1) and ν(CN)
1
(
2215 cm− for L1) modes were also modified upon
X
2
2
L
2
2
2
coordination with the CuX salts (for both CPs, respectively,
3
6
−
37
2
38
2
−
1
−1
at ∼1979 and ∼2231 cm ). The decrease of ∼30 cm for
ν(CC) is consistent with the expected back-donation from
the electron-rich Cu(I) center. The X-ray data for CP1 and
C), (L = C /P-donor), (B-η -CC/P-donor), (η -C
C/P-donor), (S-donor/N-donor), (Se-donor/N-donor),
3
9
40
41
42
(S-donor/P-donor) ). Conversely, the cis form is extremely
rare and does not exist, unless a bridging ligand forces this type
of geometry.
2
CP2 reveals that indeed both coordination sites (η -CC and
1
1,43
CN:) are used by the Cu metals forming CP networks
In CP2, the cis geometry is obtained without
(
Figure 1). No crystallization solvent molecule was detected in
the use of a bridging ligand. To the best of our knowledge, this
feature is unique. Instead, a large chelating frame composed of
the lattice making these CPs nonporous. This trait resembles
10b
2 n
that for the 2D CP [{Cu (μ -Br) } (L2) ]
and is explained
two ←:NC−C
6
H
4
−CC branches (from two different L1
2
2
2
2
2
by the relative orientation of one of the two L2 ligands that
ligands) and one central rhomboid (η -CC)
2 2 2
Cu Br SBU
places the C H planes near parallel to the 2D plane of the CP.
play together the role of this pseudobridging assembly and bind
two Cu atoms of the rhomboid on the same face through Cu−
N links. The resulting structure of the cis-rhomboid is not
planar but rather exhibits a butterfly geometry, which has also
6
4
This geometry prevents formation of cavities susceptible to
host a solvent molecule. Conversely, the [{Cu (μ -I) }(L2) ]
4
2
4
2 n
CP exhibits cavities that can accommodate acetonitrile,
10
43
propionitrile, or methanol. In this case, all the C H planes
been observed for the other rare examples. This distortion
6
4
adopted a relative orientation rather perpendicular to the CP
plane, thus forming approximately square cavities. For both
CP1 and CP2, L1 exhibits one of the two C H planes placed
nearly flat with the 2D geometry of the CP layers. This feature
also prevents the formation of pores in the lattice.
from planarity is also consistent with the rather high degree of
flexibility of the (CuX) SBUs (X = Cl, Br, I; n = 2−8).
n
Thermal Stability and X-ray Powder Diffraction
Patterns. The thermal stability of L1, CP1, and CP2 was
evaluated by TGA (Table 2, Figure 3). The first weight losses
are noted at ∼260, ∼261, and ∼271 °C with mass loss of 3, 3,
and 19% for L1, CP1, and CP2 corresponding to the
decomposition of the ligand via the loss of CN (theory =
4%), CN (3%), and [2(CN) + (C H )] (17%),
6
4
The key features of CP1 and CP2 are that L1 exhibits major
distortions (note that the L1 ligand adopts quasi-identical
structures in both cases) and the CPs use {Cu (μ -X) } SBUs
2
2
2
exhibiting both trans- (X = I) and cis-geometries (X = Br;
Figure 2). Noteworthy, the two parameters that differ the most
from the most [Pt]-containing CPs are the C−CC angles
8
4
respectively. This thermal stability (T
considered good for a CP. The second weight losses show a
> 240 °C) is
dec
C
DOI: 10.1021/acs.inorgchem.8b00899
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Inorganic Chemistry
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Figure 1. Crystal structures of the 2D polymers CP1 (top) and CP2 (bottom): Cu = gold, Br = brown, I = purple, Pt = pale gray, P = orange, C =
gray, and N = blue. The thermal ellipsoids are represented at 50% probability, respectively. The H atoms are omitted for clarity.
very similar pattern at a plateau starting at ∼375, 355, and ∼405
C with weight loss of 32, 21, and 11% for L1, CP1, and CP2,
respectively. These weight losses correspond to the loss of two
comparison purposes with its CPs (Figure 4). L1 exhibits a
fluorescence and phosphorescence band, respectively, in the
350−450 and 450−700 nm windows (the peak positions are
indicated in Figure 4 or the figure caption). These assignments
are based on the time scale of their respective lifetimes (i.e. <90
ps and μs, respectively; see details below), their Stokes shifts
°
(
(
C H ) (theory = 33), two (C H ) (20), and one (C H )
11%) for L1, CP1, and CP2, respectively. The third weight
8 4 8 4 2 8 4
loss of 25 (26) and 12 (theory = 9%) at ∼570 and ∼510 °C
−1
correspond to the loss of I and (PMe ) for CP1 and CP2,
(1900−2400 and 6300−9800 cm , respectively), literature
2
3
44
respectively. The residual masses at temperature greater than
50 °C are 65 (theory = 63), 51 (51), and 58 (61%) for L1,
precedents on this well-known type of chromophore, and the
DFT computations below. Because L1 is found much distorted
within the 2D layer of CP1 and CP2, an optimized geometry of
L1 was computed for comparison purposes but also to correlate
its properties in solution.
8
CP1, and CP2, respectively.
For the purpose of the photophysical measurements, the
powdery samples were analyzed by powder X-ray diffraction
(
PXRD; Figure 3). The experimental traces matched well the
calculated ones based on the single-crystal data. No other phase
crystalline nor amorphous, generally depicted by a large halo)
For characterization purposes, the optimized geometries of
L1 in the ground (S ) and lowest triplet excited states (T ) to
define its properties in solution are presented in Figure 5. The
0
1
(
was detected.
computed dihedral angles made by the C H aromatics and the
6
4
Photophysical Characterization of L1. L1 was first
examined in both solution and solid state at 298 and 77 K for
PtP C planes are 90° and 0°, respectively, for the S and T
states. Both geometries agree with previous DFT investigations
2
2
0
1
D
DOI: 10.1021/acs.inorgchem.8b00899
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Inorganic Chemistry
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Figure 2. X-ray structure of L1 within the CP1 and CP2 lattice. (top) View of a segment of the 2D CP1. The H atoms are hidden for clarity.
Selected bond lengths (Å) and angles (deg): Cu1···Cu2 3.5786(4), Cu1−I1 2.7497(4), Cu2−I1 2.7074(4), Cu2−N2 1.981(4), Cu1−N1 1.974(4),
I1···I1 4.1136(4); Cu2−I1−Cu1 81.954(15), N2−Cu2−I1 105.43(7), I1−Cu2−I1#7 98.88(2), N2−Cu2−I1#7 105.43(7). Symmetry
transformations used to generate equivalent atoms: #7 x, −y + 1/2, z. (bottom) View of a segment of the 2D CP2. The H atoms are hidden
for clarity. Selected bond lengths (Å) and angles (deg): Cu1···Cu2 3.191(6), Cu1−Br1 2.544(4), Cu2−Br1 2.577(4), Cu1−N2 1.949(19), Cu2−N1
2
.003(17), Br1······Br1 3.899(6); Cu1−Br1−Cu2 77.08(13), N2#6−Cu1−Br1 101.9(3), Br1−Cu2−Br1#7 98.26(16), Br1#7−Cu1−Br1 100.00(16),
N1#2−Cu2−Br1#7 103.2(3). Symmetry transformations used to generate equivalent atoms: #6 x + 1/2, −y + 1/2, −z + 5/2; #7 x, −y + 1/2, z.
4
5
46
Table 1. Interplanar C H ···C H Distances (d), C−CC
on other related complexes in their S0 and T1 states. This
computational outcome corroborates the recently reported very
6
4
6
4
a
Angles, and Measured Angles between Planes A, B, and C
47
low-energy barrier to rotation around the Pt−C bonds, which
is also well-perceived in Tables 1 and S3. The bond angles
∠
C−CC and ∠Pt−CC are rather linear for the
uncoordinated ligand L1.
dihedral angle
The molecular orbital (MO) representations for the highest-
occupied molecular orbital (HOMO) and lowest-unoccupied
molecular orbital (LUMO) for S0 analysis and lowest-
semioccupied (LSOMO) and highest-semioccupied molecular
a
a
∠
C−CC
∠Pt−CC
A/B
B/C
A/C
(
deg)
(deg)
(deg) (deg) (deg)
dimension-CP
1
75.2 (1.9)
175.0 (2.0)
38.7
90
33.9
31.0
31.4
4.8 0D-L1(X′ = CN;
R = Me)
orbitals (HSOMO) for T study are presented in Figure 5. The
1
1
1
75.0 (2.0)
57.7 (4)
178.0 (1.6)
174.2 (4)
relative atomic contributions distributed over various molecular
90
2D-[(Cu I ) L1]
2 2 2 n
(
CP1)
fragments (CC, C H CN, Pt(PMe ) ) for the frontier MOs
6
4
3 2
1
1
61.8 (4)
59 (2)
172.7 (4)
174 (2)
are provided in Tables 3 and 4 for the S and T states,
0 1
90
90
2D-
respectively. Qualitatively, these computational results for both
[
(
(Cu Br ) L1]
2
2
2
n
the optimized geometry of L1 and its X-ray structure indicate
CP2)
1
1
that the nature of both excited states (S : (HOMO) (LUMO),
1
58 (2)
174 (2)
1
l
1
a
T : (LSOMO) (HSOMO)) are intraligand ππ* (CNC H C
1
6
4
The esd values are in parentheses.
C) mixed with metal-to-ligand charge transfer (MLCT), which
45,46
is consistent with the previous conclusions.
This compar-
E
DOI: 10.1021/acs.inorgchem.8b00899
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Inorganic Chemistry
Article
a
Table 2. TGA Data for L1, CP1, and CP2
T (°C), Δmass; exp (calc%)
T (°C), Δmass; exp (calc%)
∼375, 32 (33) [(C H ) ]
T (°C), Δmass; exp (calc%)
T (°C), Δmass; exp (calc%)
L1
∼260, 3 (4) [CN]
>850, 65 (63)
>850, 51 (51)
>850, 58 (63)
8
4 2
CP1
CP2
∼261, 3 (3) [CN]
∼355, 21 (20) [(C H ) ]
∼570, 25 (26) [I2]
∼510, 12 (9) [PMe3]
8
4 2
∼271, 19 (17) [(CN) + (C H )]
∼405, 11 (11) [(C H )]
2
8
4
8
4
a
The proposed fragment losses are placed inside the brackets.
Figure 3. (left) Comparison of the experimental (red) and calculated (black) PXRD patterns for L1, CP1, and CP2. (right) TGA traces (black) and
its 1st derivative (gray) for L1, CP1, and CP2.
ison suggests that the nature of the excited states of L1 is
influenced slightly by minor structural distortions.
obviously unknown. To overcome this problem, a correction
factor is applied defined as the difference in calculated (445
nm) and experimental (522 nm) positions of the maximum
Moreover, TD-DFT computations (Table 5) place the S −S
0
1
−1
electronic transitions at ∼343 and ∼373 nm, respectively, for
L1 (in its optimized geometry using a THF solvent field) and
in the crystal lattice (no geometry optimization is applied).
These values compare well to the absorption features in
solution and in the solid state (λmax ≈ 350 nm; Figure 4).
Similarly, the position of the phosphorescence of L1 was
predicted by DFT by calculating the energy difference between
the total energy of L1 in the S and T states (Table 6). The
(3346 cm ).
The phosphorescence maxima and lifetimes τ values for L1
P
in the solid state are placed in Table 7. Expectedly, the peak
10b
maxima compare to those for L2,
and in both cases,
biexponential kinetics are depicted (as well as in glassy matrices
at 77 K; see the τ data in the caption of Figure 4). The reason
P
4
8
for this complexity was recently outlined in detail. In short,
the [Pt] motif exhibits a high degree of rotational flexibility
around the Pt−CC bonds and often the presence of different
dihedral angles (as listed in Table 1 and Table S3); different
site in the lattice (more than one molecule per unit cell or
placed at the surface of the crystal) leads to different specific τP
values. In glassy matrices (i.e., 77 K), computations
demonstrated that, in fact, multiple trapped stable conforma-
0
1
position of the T → S electronic transition calculated for L1
1
0
in 2MeTHF is 499 nm (using the optimized geometries), which
compares reasonably with the experimental positions of 473
nm. However, the calculated one for L1 in the solid state is 445
nm (using strictly the X-ray data) and does not match that in
the solid state (522 nm). The main reason is that this
calculation does not take into account the true structure in the
tions exist, again each exhibiting their own τ values. The
P
triplet state, as geometry optimization (here in the T state) is
simply not possible in the solid state for obvious steric reasons.
The true geometry within the constraint of a crystal lattice is
reason stems from the shape of the Pt d orbitals that could
accommodate the sp-hybridized CC groups. In brief, in these
experimental conditions, multiple exponential emission decays
1
F
DOI: 10.1021/acs.inorgchem.8b00899
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Inorganic Chemistry
Article
Figure 4. Emission (red), excitation (blue), and absorption (black) spectra of L1 in solid state [ss] (top) and in 2MeTHF [sol] (bottom) at 298 K
(
∑
left) and 77 K (right). The lifetime τ of L1 in 2MeTHF at 77 K is 70.3 μs (B : 0.0551; f : 60%) and 120 μs (B : 0.0221; f : 40%; f (%) = (B τ )/
P 1 1 2 2 i i i
2
2
(B τ ) × 100; I (t) = B exp(−t/τ ) + B exp(−t/τ ) + B exp(−t/τ ) + ...; χ = 1.027), and at 298 K, it is 0.77 μs (f : 99.73%; χ = 1.088). The
i
i
P
1
1
2
2
3
3
i
presence of a double exponential is explained below. The fluorescence lifetimes τ are below the IRF of the instrument (i.e., <90 ps). The emission
F
spectra for solid samples are limited by glassware (cutoff at 400 nm). The position of the weak fluorescence signals (λ ) are as follow: ∼400, 374, and
F
3
75 nm for L1 in the solid state at 298 K and in solution at 298 and 77 K, respectively.
Table 3. Relative Atomic Contributions (%) of the Various
Fragments to the Frontier MOs of L1 in Its Optimized
a
Geometry and the X-ray Structure
opt geo
H-2
H-1
HOMO LUMO
L+1
L+2
2
2
(CC)
36.9
37.4
25.7
H-2
47.7
13.8
38.5
H-1
41.1
34.3
24.6
11.0
81.4
7.6
8.6
13.0
9.7
(C H CN)
85.8
5.5
6
4
Pt(PMe3)2
X-ray
77.3
L+2
HOMO LUMO
L+1
2
2
(CC)
35.1
52.0
12.8
54.6
12.7
32.7
43.4
30.0
26.7
10.7
72.3
16.9
12.0
73.7
14.3
1.0
(C H CN)
90.4
8.5
6
4
Pt(PMe3)2
a
H = HOMO, L = LUMO; the values in bold represent contributions
greater than 35%. See Tables S4 and S5 for more MOs.
From a comparison with other related CPs containing the
Pt]-type ligands, CP1 and CP2 at 298 K exhibit the largest
[
emission quantum yields Φ (∼30%) and the most red-shifted
P
peak maxima (640 and 650 nm) of the whole series (Table S8).
Moreover, these CPs exhibit particularly broad emission bands
(i.e., full width at half-maximum (fwhm) ranging from 3000 to
Figure 5. (upper) Representations of the HOMO, LUMO, LSOMO,
and HSOMO of L1 (optimized geometry (left) and X-ray structure
−
1
(
right); energies in eV; see Figures S6 and S7 for more MOs). (lower)
5
000 cm ). Conversely, their emission lifetime values τ
P
Bar graph reporting the calculated oscillator strength (f) and
calculated positions (by TD-DFT) of the first 100 electronic
transitions for L1 from its optimized geometry using a THF solvent
field (left) and X-ray structure. The black line is generated by assigning
compare relatively favorably with these related species. The
emission time scale (μs) and particularly large Stokes shifts
−1
(
11 900−13 400 cm ) indicate the presence of triplet
−1
emissions. Biexponential emission decays are also observed,
but due to the unavoidable presence of different sites of
occupations in the solids (e.g., core and surface sites) as
previously well-demonstrated for other related [Pt]-com-
an arbitrary fwhm of 1000 cm to each transition.
48
(generally two or three) are to be expected. In fluid solution at
pounds.
room temperature, the decay is monoexponential (τ = 0.77 μs;
DFT and TD-DFT Calculations. Fragments of the X-ray
structures were used as models (i.e., input files) for DFT and
TD-DFT computations to provide information on the nature of
the S and emissive T excited states for CP1 and CP2.
The visual representations of the frontier MOs (HOMO and
LUMO for singlet; LSOMO and HSOMO for triplet) for CP1
and CP2 are shown in Figure 7, and the relative atomic
P
±
5%), which is consistent with the low energy of rotation
around the Pt−CC bond.
Photophysical Properties of CP1 and CP2. The
absorption, excitation, and emission spectra of CP1 and CP2
are shown in Figure 6, and the emission data are summarized in
Table 7.
1
1
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Inorganic Chemistry
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a
Table 4. Relative Atomic Contributions (%) of the Various Fragments to the Semi-Occupied MOs of L1 in Its Lowest-Energy
b
Triplet Excited State
optimized geometry
X-ray structure
fragments
LS-1
LSOMO
HSOMO
HS+1
LS-1
LSOMO
HSOMO
HS+1
2
2
(CC)
55.3
12.8
31.8
35.8
41.1
23.1
16.3
75.7
8.0
10.4
80.1
9.5
54.9
12.0
33.1
44.1
30.5
25.3
10.4
83.3
6.3
14.5
61.1
24.5
(C H CN)
6
4
Pt(PMe3)2
a
b
Optimized a with THF solvent field. HS = HSOMO, LS = LSOMO; the values in bold represent contributions greater than 40%.
Table 5. Calculated Positions, Oscillator Strengths (f), and Major Contributions of the First Five Singlet−Singlet Electronic
a
Transitions for L1
opt geo
λ (nm)
f
major contributions (%)
H-1→L (73), H→L (19)
1
342.8
328.5
326.1
306.4
302.1
0.103
0.085
0.763
0.054
0.015
2
H-1→L+1 (63), H→L (12), H→L+1 (11)
H-1→L (13), H-1→L+1 (12), H→L (60)
H-2→L (12), H-1→L+1 (11), H→L+1 (51), H→L+2 (20)
H→L+1 (12), H→L+2 (69)
3
4
5
X-ray
λ (nm)
f
major contributions (%)
1
2
3
4
5
372.6
354.3
324.7
307.9
299.4
0.922
0.067
0.150
0.040
0.113
H→L (91)
H-1→L (74), H-1→L+1 (18)
H-2→L (13), H-1→L+1 (12), H→L+1 (64)
H-1→L (12), H-1→L+1 (57), H→L+1 (17)
H-2→LUMO (67), HOMO→L+1 (11)
a
Optimized geometry and X-ray structure. See Tables S6 and S7 for the first 100 electronic transitions.
Table 6. Calculated T −S Energy Gaps and Calculated
states. The main conclusion of these computations is that the
low-energy spin-allowed electronic transitions generate low-
lying metal/halide-to-ligand charge transfer ( M/XLCT*)
1
0
a
Positions (λ ) of the T Emissions for L1, CP1, and CP2
max
1
1
calcd
exp
λmax
(77
K;
corr
calcd
λmax
excited states. Concurrently, the T excited states (built upon
λmax
1
3
T −S
T →
the LSOMO and HSOMO) are also best described by M/
1
0
1
gap (eV,
S
0
T →S
1
0
compound cm−1
nm) T −S gap −3346 cm−1
b
XLCT*. Similarly, TD-DFT computations place the lowest-
energy electronic transitions in the vicinity of 500 nm with
weak f values (Table 9), precisely where the absorption band
starts (see black lines in Figure 6).
In addition, by tracing the calculated oscillator strengths for
the first 80 singlet−singlet electronic transitions as a function of
their calculated positions, simulated spectra can be generated
)
(nm)
(nm)
1
0
L1 opt
2.48,
20 003
499
473
522
590
584
geo
L1 X-ray
2.79,
2 503
445
455
465
19 157
18 632
18 159
522
537
2
CP1 X-ray 2.73,
21 978
CP2 X-ray 2.67,
551
(
3
Figure 8). Most of these 80 components are located between
50 and 450 nm, which means that, by considering their
21 505
a
b
Optimized geometry using a THF solvent field and X-ray data. A
vibronic progressions, this spectral segment is predicted to be
filled with unresolved components. This is precisely what is
depicted in Figure 6, where the absorption envelope is
essentially broad and unresolved in this 350−450 nm region.
Noteworthy, the calculations of the positions of the S → T
correction factor was applied due to the impossibility to optimize the
geometry in the solid state. This factor is based on the well-defined
emission of L1 (using X-ray data) as calculated T −S gap −
1
0
−
1
experimental T −S gap of L1: 22 503 − 19 157 = 3346 cm .
1
0
0
1
electronic transitions using the X-ray data of CP1 and CP2
matrices are, respectively, 455 and 465 nm (Table 6). These
calculated positions need to be corrected for the fact that no
geometry optimization was applied. This correction factor
contributions of the various fragments building these models to
the frontier MOs are placed in Table 8. By examining the low-
energy electronic transitions (see, e.g., Table 9), one can
monitor the change in atomic contributions in the excited
−1
(3346 cm ) was deduced using L1 (see above) and is applied
Table 7. Comparison of the Phosphorescence Positions and τ Data for L1, CP1, and CP2
P
2
98 K
77 K
a
b
χ2
c
a
b
χ2
λmax (nm)
Bi
τP (μs)
Φe (%) λmax (nm)
Bi
τP (μs)
tw
0
0
2
2
D-L1 (2MeTHF solution)
483
473
650
640
0.77
1.088
1.156
1.052
1.034
473
0.0551 0.0221
0.0071 0.0393
0.0292 0.0013
0.0062 0.0084
70.3 120
32.5 75.0
30.4 67.2
15.0 51.0
1.027
1.066
1.049
1.019
tw
D-L1 (solid state)
0.0876 0.1342
0.0690 0.0092
0.0156 0.0081
0.46 1.87
0.64 7.10
4.27 10.6
26
32
28
522
590
584
tw
D-[(Cu I ) L1] (CP1)
2
2
2
n
tw
D-[(Cu Br ) L1] (CP2)
2
2
2
n
a
b
c
I (t) = B exp(−t/τ ) + B exp(−t/τ ) + B exp(−t/τ ) + .... The uncertainties are ±5%. The uncertainties are ±10% based on multiple
P
1
1
2
2
3
3
measurements.
H
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Figure 6. Emission (red), excitation (blue), and absorption (reflectance; black) spectra of CP1 (top) and CP2 (bottom) in solid state at 298 (left)
and 77 K (right). The absorption features spreading up to 500 nm in CP1 and CP2 are S → S absorptions based on TD-DFT computations below.
0
1
at 650 and 640 nm at 298 K) and spread toward the near-IR
(
Figure 6).
The S −T Energy Gaps. DFT (Table 9; S → S , 510 and
1
1
0
1
5
04 nm) and TD-DFT (Table 6; S → T , 537 and 551 nm)
0 1
clearly predict a very small S −T energy gap. Experimentally,
1
1
time-resolved spectroscopy shows no evidence for the existence
of other short-lived components (here sought in the pico-
second time scale (i.e., ≤90 ps) for this type of metalloligand),
indicating that no fluorescence is detected. This observation is
fully consistent with the heavy atom effect associated with the
presence of Cu X rhomboids (X = Br, I) directly coordinated
2
2
onto L1. These two observations combined are also
corroborated by examining the unresolved (0−0) origins of
both the absorption band on the low-energy side and the
phosphorescence on the high-energy side. Indeed, both origins
appear in the vicinity of 500 nm with no or almost no spectral
overlap between the two (Figure 6). This is also consistent with
−1
the large Stokes shifts (11 900−13 400 cm ). Concurrently,
L1 in 2MeTHF exhibits a well-defined fluorescence band at 375
nm, and this overlaps clearly with the absorption (Figure 4). All
these observations and comparisons indicate that indeed the
S −T energy gaps must be small.
1
1
Usually, small S −T energy gaps are associated with
1
1
perpendicularly oriented singlet- and triplet-state manifolds,
where the two unpaired electrons are located (like in nπ*
states). The representations of the frontier MOs illustrate well
with this orientation situation (Figure 7) and bear their
importance for the interpretation of the excited-state properties
of these novel CPs. In conclusion, all of these computations
and comparisons support the 1 M/XLCT* assignments, which
,3
are unsurprisingly essentially the same as that was made for the
Figure 7. Representations of the frontier MOs for CP1 (top) and CP2
bottom). See Figures S8 and S9 for more MOs.
10b
other related CPs listed in Table S8.
However, these
(
computational predictions and experimental observations of a
small S −T energy gaps are new.
1
1
Structure−Property Relationship. Both CP1 and CP2
for CP1 and CP2 (Table 6). After correction, the predicted
positions of the T → S transitions are, respectively, 537 and
exhibit the most red-shifted triplet emissions among all the CPs
using the trans-Pt(PMe
)
(CCC
H X) metalloligands.
1
0
3
2
6 4 2
2
5
51 nm for CP1 and CP2. These values fall perfectly within the
range where the phosphorescence bands appear (i.e., starting at
00 nm, then exhibiting maxima at 590 and 584 nm at 77 K and
These new CPs are built upon Cu-(η -CC) and Cu−X
coordinations (X = CN, SMe), and L1 undergoes stress from
both fragments simultaneously, inducing distortions along the
5
I
DOI: 10.1021/acs.inorgchem.8b00899
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Inorganic Chemistry
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a
Table 8. Relative Atomic Contributions of the Various Fragments to the CP Frontier MOs
singlet (in %)
triplet (in %)
CP1
L1
Cu
I
H − 1
6.8
HOMO
6.8
LUMO
91.4
7.8
L + 1
96.9
2.8
LS − 1
9.0
LSOMO
HSOMO
88.3
HS + 1
36.1
97.1
2.4
31.3
61.9
H − 1
24.6
31.4
30.3
34.2
10.7
61.7
0.8
0.3
60.7
29.7
1.0
0.4
CP2
L1
Cu
Br
HOMO
11.0
LUMO
97.3
2.2
L + 1
94.9
4.5
LS − 1
31.0
LSOMO
13.6
HSOMO
94.0
HS + 1
97.8
2.0
44.4
31.0
41.9
37.9
38.3
5.0
47.1
0.5
0.5
31.1
48.1
1.0
0.2
a
Major contributions in bold. See Supporting Information for more MOs in the singlet state. See Tables S9 and S10 for more MOs.
Table 9. Calculated Positions, Oscillator Strength (f), and Major Contributions of the First Two Singlet−Singlet Electronic
a
Transitions for CP1 and CP2
λ (nm)
f
major contributions (%)
CP1
CP2
5
5
10.0
02.2
0.0007
0.0004
HOMO−1→LUMO (85)
HOMO→LUMO (71), HOMO→LUMO+1 (18)
5
03.7
02.2
0.0005
0.0364
HOMO→LUMO (39), HOMO→LUMO+1 (58)
5
HOMO−1→LUMO (42), HOMO−1→LUMO+1 (55)
a
See Tables S11 and S12 for the first 80 electronic transitions.
CONCLUSION
■
This work demonstrated that this new organometallic ligand
L1, belonging to a family of complexes often presented as rigid
sticks, can be significantly distorted by rather soft and usually
readily adaptable (CuX) SBUs (X = halide, here Br and I; n =
2n
1
, 2, 3, ...). This adaptability was demonstrated by the presence
of two geometries for the SBUs formed: trans-Cu I (common)
2
2
and cis-Cu Br (extremely rare). These distortions for L1 turn
2
2
Figure 8. Bar graph reporting the calculated oscillator strength and
calculated position of the first 80 electronic transitions calculated by
TD-DFT for CP1 and CP2 (bar graph; f = computed oscillator
strength). The black line is generated by assigning an fwhm = 1000
out to be the largest ever observed for this category of
complexes (denoted [Pt]), and yet, the TGA traces indicated a
rather good thermal stability (Tdec > 250 °C). The two new
−1
cm to the transition.
CPs are also very luminescent (Φ ≈ 30%) and exhibit the most
e
red-shifted maxima (650 nm) at 298 K. The lowest-energy
excited states are 1 M/XLCT* based upon DFT and TD-DFT
computations and comparisons of experimental findings, but
very interestingly, the S −T energy gaps are predicted to be
,3
∠
(C−CC) bond angles and dihedral angles (θ ) made by
da
1
1
the planes A, B, and C (Table 1). The optimized geometry of
unusually small. The main conclusion is that the presence of
2
L1 (in the gas phase) in its triplet state exhibits all three
dihedral angles θ = 0° (see above). Consequently, deviations
from this value represent a distortion. The most relevant way to
quantify this distortion for comparison purposes is to add all
Cu(η -CC) binding in the [Pt] ligands, which is more
10a,b
da
favored over the Cu−S link,
distorts its scaffolding in
various extents as illustrated in Table 1 (and Table S3). This
feature means that the preparation of porous materials,
including metal−organic frameworks, is impeded by this
three (∑θ ). By comparing the phosphorescence maxima with
da
2
∠
(C−CC) bond angles and ∑θda (Table 10), a clear
Cu(η -CC) trait. To avoid such distortions and the
2
correlation is depicted. In brief, more distorted L1 is, more red-
undesired Cu(η -CC) interactions, steric constraints about
3
shifted the (M/XLCT)* emission is.
the Pt(II) atom must be considered in future designs.
Table 10. Comparison of the Emission Maxima with Structural Parameters of the 2D-CPs
a
b
b
c
2
D-CP
ref
λmax (nm) 298, 77 K
av ∠(C−CC) (deg)
av ∠ (Pt−CC) (deg)
∑θda (deg)
[
[
[
[
[
(Cu I ) L1] (CP1)
tw
tw
650, 590
640, 584
603, 575
586, 571
568, 555
159.8
158.5
161.0
162.0
163.3
173.5
174
211
211
80
2
2
2
n
(Cu Br ) L1] (CP2)
2
2
2
n
(Cu Br )L2]
10b
10b
10b
173.6
173.9
175.5
2
2
n
(Cu Br )L2]
63
2
2
n
(Cu I )L2·PrCN]
n
72
4
4
a
b
c
tw = this work. Average (av) angles from Table 1 or ref 10b. Sums of the dihedral angles from Table 1 or ref 10b. Note that the esd values are
placed with the data in Table 1 or ref 10b.
J
DOI: 10.1021/acs.inorgchem.8b00899
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
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ASSOCIATED CONTENT
Supporting Information
■
*
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The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.8b00899.
Stability and reactivity of grafted Cr(CO) species on MOF linkers: a
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X-ray data, IR, H and NMR P spectra, representations
of the frontier MOs, relative atomic contributions of the
various fragments to the frontier MOs, calculated
positions, oscillator strengths, and major contributions
of the first 100 or 80 singlet−singlet electronic
transitions of L1, CP1, and CP2, comparison of the
interplanar C H ···C H distances, C−CC angles and
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̌
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̌
́
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of the emission positions and τ data for L1, CP1, and
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charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
Synthesis of a New Organometallic Ligand, 1-Ferrocenyl-3-(5-
bromopyridyl)-prop-3-enol-1-one and Its Heteronuclear Coordination
Polymer, {Cu[1-ferrocenyl-3-(5-bromopyridyl)prop-1,3-dionate] } .
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AUTHOR INFORMATION
Corresponding Author
E-mail: Pierre.Harvey@USherbrooke.ca.
ORCID
■
*
(6) (a) Cooper, T. M.; Burke, A. R.; Krein, D. M.; Ziolo, R. F.; Arias,
E.; Moggio, I.; Fratini, A.; Garbovskiy, Y.; Glushchenko, A. V.
Daniel Fortin: 0000-0002-0223-6362
Pierre D. Harvey: 0000-0002-6809-1629
Notes
Cholesteric liquid crystal glass platinum acetylides. MRS Online Proc.
Libr. 2014, 1698, 820. (b) Klovekorn, P.; Munch, J. Variable
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stimulated Brillouin scattering pulse compressor for nonlinear optical
measurements. Appl. Opt. 1997, 36, 5913−5917. (c) Bruce, D. W.;
Lea, M. S.; Marsden, J. R. The synthesis and mesomorphism of some
acetylide complexes of platinum (II) and palladium (II). Mol. Cryst.
Liq. Cryst. Sci. Technol., Sect. A 1996, 275, 183−194.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the Natural Sciences and
Engineering Research Council of Canada, the Fonds de
■
(7) (a) Durand, R. J.; Gauthier, S.; Achelle, S.; Kahlal, S.; Saillard, J.
Y.; Barsella, A.; Wojcik, L.; Le Poul, N.; Robin-Le Guen, F.
Incorporation of a platinum center in the pi-conjugated core of
push−pull chromophores for nonlinear optics (NLO). Dalton Trans.
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Marinotto, D.; Oliveri, I. P.; Righetto, S.; Lobello, M. G.; De Angelis,
F. Unexpectedly high second-order nonlinear optical properties of
simple Ru and Pt alkynyl complexes as an analytical springboard for
NLO-active polymer films. Chem. Commun. 2014, 50, 7986−7989.
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