Inorganic Chemistry
ARTICLE
range of 470À700 nm with several peaks and exhibit somewhat
similar characteristics regardless of the carboxylate groups at-
tached to the phenylethynide ligands. The solid sample of 1
displays a broad band with three peaks at 523, 567, and 614 nm,
and the maximum is at 567 nm on excitation at 370 nm. There are
two peaks located at 528 and 564 nm and two shoulders around
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∼
500 and ∼620 nm for 2, and 3 exhibits one maximum peak at
5
74 nm and two shoulders at ∼500 and ∼620 nm. Their
relatively long lifetimes, 0.12, 0.20, and 0.76 ms for 1, 2, and 3,
(2) (a) Kuppler, R. J.; Timmons, D. J.; Fang, Q.; Li, J.; Makal, T. A.;
respectively, indicate phosphoresence characteristics. For assign-
Young, M. D.; Yuan, D.; Zhao, D.; Zhuang, W.; Zhou, H.-C. Coord.
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ment purposes, the emission spectra of the ligands, HL1, H L2,
2
and H L3 were also measured (Figure S2 in the Supporting
2
Information). Obviously, these bands are somewhat similar to
that observed for complexes 1, 2, and 3 in the solid state, which
also spread in the range of 470À720 nm. These results indicate
that the emissions mainly originate from ligand-centered excited
€
N.; Choi, S.; Choi, E.; Yazaydin, A. O.; Snurr, R. Q.; O’Keeffe, M.; Kim,
J.; Yaghi, O. M. Science 2010, 329, 424–428. (e) Yuan, D.; Zhao, D.; Sun,
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5a,19
states and are not possibly related to metal centers.
There-
fore, it is reasonable to attribute these emissions as intraligand
transitions, perturbed by silver(I)-ligand interactions based on
the comparisons.
132, 15390–15398. Yi, F.-Y.; Lin, Q.-P.; Zhou, T.-H.; Mao, J.-G. Inorg.
Chem. 2010, 49, 3489–3500.
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4
7, 1326–1331. (b) Fenske, D.; Anson, C. E.; Eichh €o fer, A.; Fuhr, O.;
’
CONCLUSIONS
Ingendoh, A.; Persau, C.; Richert, C. Angew. Chem., Int. Ed. 2005,
44, 5242–5246. (c) Fenske, D.; Persau, C.; Dehnen, S.; Anson, C. E.
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T.; Person, C.; Kang, B.-S.; Sheldrick, G. M.; Fenske, D. Angew. Chem.,
Int. Ed. 2002, 41, 3818–3822. (e) Fenske, D.; Zhu, Y.; Langetepe, T.
Angew. Chem., Int. Ed. 1998, 37, 2640–2644. (f) Li, G.; Lei, Z.; Wang,
Q.-M. J. Am. Chem. Soc. 2010, 132, 17678–17679. (g) Tang, K.; Xie, X.;
Zhang, Y.; Zhao, X.; Jin, X. Chem. Commun. 2002, 1024–1025.
By utilizing mono- and dicarboxylphenylethynyes as ligands, a
series of new silver(I)-ethynide complexes have been synthesized
and structurally characterized. These kinds of complexes bearing
carboxylate groups could serve as new building units to assemble
novel silver(I)-organic networks, which exhibit diverse coordina-
tion modes and are capable of interacting with more silver(I) ions
or silver(I)-ethynide complex units compared to silver(I) pyridyl
or pyrimidylethynide complexes and thus lead to high-level
organometallic networks through silver(I)-carboxylate coordina-
tion bonds. The obtained results demonstrate that the structure
of the assembled network constructed from silver(I)-ethynide
complexes is highly dependent upon the number of carbo-
xylate groups attached to the phenylethynide ligands. In the
solid state, all the complexes synthesized in this work are emissive
at room temperature, which mainly originate from intraligand
n f π* and π f π* transitions.
(4) (a) Qiao, J.; Shi, K.; Wang, Q.-M. Angew. Chem., Int. Ed. 2010,
49, 1765–1767. (b) Bian, S.-D.; Wu, H.-B.; Wang, Q.-M. Angew. Chem.,
Int. Ed. 2009, 48, 5363–5365. (c) Bian, S.-D.; Jia, J.-H.;Wang, Q.-M. J. Am.
Chem. Soc. 2009, 131, 3422–3423. (d) Xie, Y.-P.; Mak, T. C. W. J. Am.
Chem. Soc. 2011, 133, 3760–3763. (e) Gao, G.-G.; Cheng, P.-S.; Mak,
T. C. W. J. Am. Chem. Soc. 2009, 131, 18257–18259. (f)Gruber, F.;Jansen,
M. Angew. Chem., Int. Ed. 2010, 49, 4924–4926. (g) Koshevoy, I. O.; Lin,
C.-L.; Karttunen, A. J.; Janis, J.; Haukka, M.; Tunik, S. P.; Chou, P.-T.;
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(
5) (a) Chui, S. S. Y.; Ng, M. F. Y.; Che, C.-M. Chem.—Eur. J. 2005,
’
ASSOCIATED CONTENT
11, 1739–1749. (b) Lin, Y.-Y.; Lai, S.-W.; Che, C.-M.; Cheung, K.-K.;
Zhou, Z.-Y. Organometallics 2002, 21, 2275–2282. (c) Wei, Q.-H.; Yin,
G.-Q.; Zhang, L.-Y.; Chen, Z.-N. Inorg. Chem. 2006, 45, 10371–10377.
(6) (a) Mak, T. C. W.; Zhao, L. Chem.—Asian J. 2007, 2, 456–467.
(b) Zhao, L.; Wong, W.-Y.; Mak, T. C. W. Chem.—Eur. J. 2006,
S
Supporting Information. X-ray crystallographic data for
b
1
, 2, and 3 in CIF format, packing diagram for 1, and excitation
and emission spectra for HL1, H L2, and H L3. This material is
available free of charge via the Internet at http://pubs.acs.org.
2
2
1
2, 4865–4872. (c) Zhao, L.; Zhao, X.-L.; Mak, T. C. W. Chem.—Eur.
J. 2007, 13, 5927–5936. (d) Zhao, L.; Mak, T. C. W. Organometallics
2
4
2
007, 26, 4439–4448. (e) Zang, S.-Q.; Mak, T. C. W. Inorg. Chem. 2008,
7, 7094–7105. (f) Zhao, L.; Chen, X.-D.; Mak, T. C. W. Organometallics
008, 27, 2483–2489. (g) Zang, S.-Q.; Zhao, L.; Mak, T. C. W.
’
AUTHOR INFORMATION
Corresponding Author
Organometallics 2008, 27, 2396–2398. (h) Zhao, L.; Wan, C.-Q.; Han,
J.; Chen, X.-D.; Mak, T. C. W. Chem.—Eur. J. 2008, 14, 10437–10444.
*Fax: 86-27-87543632. E-mail: tlzhang@mail.hust.edu.cn.
(i) Zang, S.-Q.; Han, J.; Mak, T. C. W. Organometallics 2009, 28,
2
677–2683. (j) Li, B.; Zang, S.-Q.; Liang, R.; Wu, Y.-J.; Mak, T. C. W.
’
ACKNOWLEDGMENT
Organometallics 2011, 30, 1710–1718.
This research was supported by the National Natural Science
(7) (a) Zhang, T.-L.; Kong, J.-X.; Hu, Y.-J.; Meng, X.-G.; Yin, H.-B.;
Hu, D.-S.; Ji, C.-P. Inorg. Chem. 2008, 47, 3144–3149. (b) Zhang, T.-L.;
Hu, Y.-J.; Kong, J.-X.; Meng, X.-G.; Dai, X.-M.; Song, H.-B. CrystEng-
Comm 2010, 12, 3027–3032.
Foundation of China (Grant No. 20871049) and the Analytical
and Testing Center, Huazhong University of Science and
Technology.
(8) Zhao, L.; Mak, T. C. W. Inorg. Chem. 2009, 48, 6480–6489.
(
9) Sun, D.; Wang, D.-F.; Han, X.-G.; Zhang, N.; Huang, R.-B.;
’
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