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INTRODUCTION
Luminescent coordination polymers have been widely studied
in recent decades, and several new materials have been
produced and tested.1 In particular, the chemisorption of
small molecules onto these materials has been shown to alter
their luminescence properties,2 prospecting potential applications as molecular sensing systems. In this context, copper(I)
coordination polymers have not been as widely explored, if
compared to other transition metal or lanthanide analogues.37
In particular, CuCN can provide interesting luminescence
properties when reacted with proper ligands. A recent
computational study described its particular structure highlighting that, conversely to many inorganic salts forming twoor three-dimensional (2D or 3D) arrays, CuCN is characterized
by one-dimensional polymer chains consisting of twocoordinated metal centers and bridging cyano ligands.8
CuCN itself is characterized by a weak luminescence.9
However, its photoluminescence emission interestingly shifts
from the near UV (392 nm) into the visible region upon the
coordination of nucleophiles, while the intensity increases by
several orders of magnitude. In some cases, small dierences in
the ligands, such as the presence of methyl or ethyl groups like
in piperazine, methylpiperazine, and ethylpiperazine, can result
in remarkable dierences in the emission color of the obtained
coordination polymers, providing several luminescence tuning
possibilities.10
Despite these promising properties, the real challenge over
the past decade has been the optimization of the synthetic
XXXX American Chemical Society
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
EXPERIMENTAL SECTION
CuCN
tu
CuCN
CuCN
mtu
mtu
CuCN
ptu
CuCN
dptu
CuCN
fptu
preparation
formula
k (H2O; r.t.; 16 h)
h (aq. sol. NaCN
saturated; 100 C; 6 h)
k (H2O; r.t.; 30 min)
h (aq. sol. NaCN
saturated; 100 C; 6 h)
k (H2O; r.t.; 25 min)
s (sol. MeCN, NaCN
saturated; 80 C; 6 h)
k (H2O; r.t.; 20 min)
s (sol. MeCN, NaCN
saturated; 80 C; 6 h)
k (H2O; r.t.; 30 min)
s (sol. MeCN, NaCN
saturated; 80 C; 6 h)
yield
(%)
[(CuCN)2(tu)]n
95
45
[(CuCN)5(mtu)3]n
[(CuCN)3(mtu)2]n
96
40
[CuCN(ptu)]n
98
31
[CuCN(dptu)]n
98
41
[(CuCN)3(fptu)2]n
98
50
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
Figure 2. XRSCD structure of [CuCN(ptu)]n: (a) 1D coordination polymer along the a axis (hydrogen atoms omitted for clarity); (b) asymmetric
unit.
Figure 3. XRSCD structure of [CuCN(dptu)]n: (a) 1D coordination polymer along the a axis; (b) asymmetric unit.
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
Table 2. 1H and 13C Chemical Shifts () with Assignments for All Compounds and Pure Ligandsa
compound
tu
[(CuCN)2(tu)]n
mtu
[(CuCN)5(mtu)3]n
[(CuCN)3(mtu)2]n
ptu
[CuCN(ptu)]n
dptu
[CuCN(dptu)]n
fptu
[(CuCN)3(fptu)2]n
13
CS
CS
CN
CS
CH3
CS
CH3
CN
CS
CH3
CN
CS
Cq
CHAr
CS
Cq
CHAr
CN
CS
Cq
CHAr
CS
Cq
CHAr
CN
CS
CF
Cq
CHAr
CS
CF
Cq
CHAr
CN
[ppm]
[ppm]
NH2
NH2
8.2/7.0
6.5/5.6(sh)
1
1
NH2/NH
CH3
NH2/NH
7.7
2.5
7.5
CH3
NH2/NH
3.0
7.2
CH3
NH2
NH
CHAr
NH2/NH
3.9(sh)/3.22
3.2
4.3
6.6/9.0sh
3.6
CHAr
7.0
NH
CHAr
3.1
6.6
NH
3.4
CHAr
5.9
NH2
NH
CHAr
2.5sh
6.0
9.3sh
NH2/NH
3.9/4.6
CHAr
6.7/8.8sh
181.0
170.8
bb from 160.1 to 144.0
179.6/179.2/178.6
32.3(sh)/32.0/29.8(sh)/29.4
174.4
33.5/31.3
bb from 163.5 to 152.8
174.8/169.3
34.2
164.8/140.1
179.0
136.0
133.6/131.4/126.2
175.1/171.8
136.7
133.3/131.5/130.0/127.4/124.8/123.8/121.8
bb from 162.4 to 148.5
185.4
140.1
132.5/129.7/129.0 (sh)127.9/125.9
177.3
136.5
132.6/131.8/128.5/127.2/126.1
bb from164.8 to 148.7
184.9/182.1
162.5/160.1/157.5
132.1/130.2
123.8/114.8/112.5/106.8
177.6/173.9
163.6/161.2159.1156.8
131.0
119.2/113.1/109.1/105.9
bb from 187.0 to 146.0
The number of independent thiourea ligands (Z) is also reported. bb: broad band; sh: shoulder.
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
Tw
65.3, 111.8
Ttrans
Tfus
Tdec
185.2, 281.7
146.5
191.8
453
172.6
271.8
125.3
216.0
270.7
171.1
166.8
158.6
168.2
176.6
170.2
453
183.6
271.8
199.8
216.0
270.7
171.1
166.8
158.6
168.2
176.6
170.2
131.0
211.4
143.1, 154.9
68.6, 111.3
70.1, 112.4
emission
max
[nm]
[(CuCN)2(tu)]n
350
398, 465
[(CuCN)5(mtu)3]n
[(CuCN)3(mtu)2]n
[CuCN(ptu)]n
[CuCN(dptu)]n
[(CuCN)3(fptu)2]n
363
352
355
358
360
448
436
433
448
449
compound
Stokes
shift
[cm1]
3445,
7066
5227
5473
5074
5611
5505
[s]
<0.01
17.7
0.19
0.033
0.082
0.030
0.12
7.8
2.9
2.9
2.8
3.2
CONCLUSIONS
In summary, we have described the synthesis and characterization of six new coordination polymers based on copper(I)
I
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
Notes
ACKNOWLEDGMENTS
We are indebted to Prof. L. Celi for the elemental analyses.
ABBREVIATIONS
SSNMR, solid state nuclear magnetic resonance; DSC,
dierential scanning calorimetry; TGA, thermogravimetric
analysis; XRPD, X-ray powder diraction; XRSCD, X-ray
single crystal diraction; tu, thiourea; mtu, N-methylthiourea;
ptu, N-phenylthiourea; dptu, N,N-diphenylthiourea; fptu, 2,4diuorophenylthiourea
ASSOCIATED CONTENT
S Supporting Information
*
REFERENCES
AUTHOR INFORMATION
Corresponding Authors
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/acs.cgd.5b00352
Cryst. Growth Des. XXXX, XXX, XXXXXX