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Cu-1-hexynyl: Yellow powder (0.97 g, 74%). Anal. Calcd for C6H9Cu1:
C 49.81, H 6.27%, Found: C 49.59, H 6.06%.
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Scheme 2. Formation of copper acetylide. (i) CuI, Et3N, acetonitrile. (ii) CuCl,
NH3aq+EtOH.
General Procedure for the Recrystallization of Copper
Acetylide
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A 1 M solution of trimethylphosphine in THF (8.0 mmol, 8 ml) was
added to a suspension of CuÀ C�CÀ R (6 mmol) in dichloromethane
(50 ml). The solution was stirred for 1 h in the dark, and then the
solution was filtered. The filtrate was evaporated without heating,
and the precipitate was dissolved in a minimum amount of toluene.
Then, the solution was diluted with 300 ml of appropriate solvent
and incubated overnight. The precipitate of CuÀ C�CÀ R was
filtered, washed with a small amount of ethanol and diethyl ether
and dried in vacuo.
Cu-m-chlorophenylacetylide: Yellow powder (0.48 g, 83%). νC�C
1932 cmÀ 1 (ΔνC�C =À 182 cmÀ 1). Anal. Calcd for C8H4Cl1Cu1: C 48.26,
H 2.02%, Found: C 47.95, H 1.77%.
=
Cu-p-tBu-phenylacetylide: Yellow powder (0.46 g, 72%). νC�C
=
1909 cmÀ 1 (ΔνC�C =À 197 cmÀ 1). Anal. Calcd for C12H13Cu1: C 65.28, H
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5.93%, Found: C 65.41, H 5.69%.
Cu-4-ethynylbiphenyl: Yellow powder (0.63 g, 90%). νC�C
=
1927 cmÀ 1 (ΔνC�C =À 179 cmÀ 1). Anal. Calcd for C14H9Cu1: C 69.84, H
3.77%, Found: C 69.76, H 4.05%.
Cu-methyl propargyl ether: Diluted with acetonitrile, yellow powder
(0.08 g, 10%). Anal. Calcd for C4H5Cu1O1: C 36.22, H 3.80%, Found: C
36.14, H 3.52%.
Cu-propynyl: Yellow powder (0.23 g, 77%).
ν
C�C =2034 cmÀ 1
(ΔνC�C =À 126 cmÀ 1). Anal. Calcd for C3H3Cu1: C 35.12, H 2.95%,
Found: C 34.98, H 2.63%.
Cu-4-phenyl-1-butynyl: Diluted with acetone, yellow powder
(0.15 g, 13%). Anal. Calcd for C10H9Cu1: C 62.32, H 4.71%, Found: C
62.59, H 4.38%.
Cu-1-pentynyl: Yellow powder (0.28 g, 74%).
ν
C�C =1939 cmÀ 1
(ΔνC�C =À 181 cmÀ 1). Anal. Calcd for C5H7Cu1: C 45.96, H 5.40%,
Found: C 46.04, H 5.72%.
Cu-phenyl propargyl sulfide: Diluted with 1:1 toluene/chloroform,
yellow powder (0.14 g, 11%). Anal. Calcd for C9H7Cu1S1: C 51.29, H
3.35%, Found: C 51.53, H 3.56%.
Cu-1-hexynyl: Yellow powder (0.36 g, 86%).
ν
C�C =1926 cmÀ 1
(ΔνC�C =À 200 cmÀ 1). Anal. Calcd for C6H9Cu1: C 49.81, H 6.27%,
Found: C 49.78, H 6.32%.
Cu-9-ethynylphenanthrene: Diluted with hexane, yellow powder
(0.24 g, 15%). Anal. Calcd for C16H9Cu1: C 72.58, H 3.43%, Found: C
72.77, H 3.69%.
Cu-methyl propargyl ether: Yellow powder (0.31 g, 81%). νC�C
=
1924 cmÀ 1 (ΔνC�C =À 200 cmÀ 1). Anal. Calcd for C4H5Cu1O1: C 36.22,
H 3.80%, Found: C 36.47, H 4.03%.
Measurements
Cu-4-phenyl-1-butynyl: Yellow powder (0.49 g, 88%). νC�C
=
1939 cmÀ 1 (ΔνC�C =À 178 cmÀ 1). Anal. Calcd for C10H9Cu1: C 62.32, H
SEM images were acquired using a HITACHI FE-SEM S-4700 Type-II,
where the sample was sonicated in ethanol and cast on a Si wafer.
The EPR spectrum and magnetic susceptibility of Cu-NN were
measured using a JEOL JES-TE200 X-band EPR spectrometer and a
Quantum-Design MPMS-XL SQUID magnetometer, respectively.
Fluorescence spectra of the powder samples of Cu-9-ethynylphe-
nanthrene and Cu-2-ethynyl-9,9’-spirobifluorene were measured by
a JASCO FP-8500 spectrometer with an integral sphere.
4.71%, Found: C 61.99, H 4.55%.
Cu-phenyl propargyl sulfide: Yellow powder (0.55 g, 90%). νC�C
=
1944 cmÀ 1 (ΔνC�C =À 176 cmÀ 1). Anal. Calcd for C9H7Cu1S1: C 51.29,
H 3.35%, Found: C 50.98, H 3.46%.
Cu-NN: Green powder (0.62 g, 67%). νC�C =1971 cmÀ 1 (ΔνC�C
=
À 127 cmÀ 1). Anal. Calcd for C15H16Cu1N2O2: C 56.33, H 5.04, N
8.76%, Found: C 56.42, H 5.18, N 8.59%.
Cu-9-ethynylphenanthrene: Yellow powder (0.68 g, 89%). νC�C
=
1937 cmÀ 1 (ΔνC�C =À 161 cmÀ 1). Anal. Calcd for C16H9Cu1: C 72.58, H
3.43%, Found: C 72.21, H 3.60%.
Acknowledgements
Cu-2-ethynyl-9,9’-spirobifluorene: Yellow powder (0.76 g, 65%).
ν
C�C =1942 cmÀ 1 (ΔνC�C =À 162 cmÀ 1). Anal. Calcd for C27H15Cu1: C
This work was supported in part by a grant from the SEI group
CSR foundation.
80.48, H 3.75%, Found: C 80.20, H 3.53%.
Preparation in an Aqueous Ammonia/Ethanol Mixed Solvent
Conflict of Interest
Under an Ar atmosphere, 0.89 g (9.0 mmol) of CuCl was dissolved
in a mixture of ethanol (50 ml), 28% NH3aq (12.5 ml) and H2O
(45 ml). Then, 10 mmol of ligand dissolved in 5 ml of ethanol was
added dropwise to the solution with vigorous stirring. After 1 h of
stirring at room temperature, the solution was filtered and washed
with 5% NH3aq, H2O, ethanol and diethyl ether. The obtained
powder was dried in vacuo. The IR spectra of the obtained samples
were identical to those of samples prepared in acetonitrile.
The authors declare no conflict of interest.
Keywords: alkyne ligands · copper · nanorods · organometallic
nanomaterials · functional materials
Cu-propynyl: Yellow powder (0.66 g, 71%). Anal. Calcd for C3H3Cu1:
C 35.12, H 2.95%, Found: C 34.81, H 2.60%.
[1] a) B. Wang, Q. Ru, Q. Guo, X. Chen, Z. Wang, X. Hou, S. Hu, Eur. J. Inorg.
Chem. 2017, 2017, 3729–3735; b) Y. Wang, T. Wang, P. Da, M. Xu, G.
eaau6261. d) S. M. Oh, S. B. Patil, X. Jin, S. Hwang, Chem. Eur. J., 2017,
24, 4757–4773. e) J. Wang, J. Tang, B. Ding, V. Malgras, Z. Chang, X. Hao,
Cu-1-pentynyl: Yellow powder (0.98 g, 83%). Anal. Calcd for
C5H7Cu1: C 45.96, H 5.40%, Found: C 45.62, H 5.15%.
ChemistryOpen 2019, 8, 873–878
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