Table S3† lists the molecular unit and the new unit for com-
pound 4.
Acknowledgements
This research was supported by the basic research foundation of
Jilin University (No. 200903133) and a branch of cooperation
project (No. 3R111N651412).
As mentioned in the introduction section, the acylhydrazidate-
coordinated compound is the potential photoluminescence
material, which is due to the potential presence of multi-kinds of
charge transfer paths in the complex. But just due to this, it is
difficult to attribute the emission of the compound reasonably.
Based on the previous related reports, it could be attempted to
give a simple attribution, but sometimes an attribution from
experience is not correct. For example, compound 3 exhibits a
green-light emission, whereas compound 4 exhibits a yellow-
light emission. Based on experience, the emission of the former
should be associated with the ligand, while the low energy emis-
sion of the latter should be associated with the metal center.
However, the DFT calculations for the latter indicate that the
emission is still ascribed to the charge transfer of the intra-
ligand. The DFT calculation is a good solution to understand the
emission mechanism of the compounds. The reasonable selec-
tion of the unit for the calculations is the key. The smaller unit
such as the molecular unit of compound 4 helps the calculations,
but once the small unit does not represent the whole structure,
the calculated results will deviate from the experiment results.
The larger unit could represent the whole structure, but this will
lead to difficulties for the calculations. For compound 4, that
new unit is just the maximum selection.
References
1 (a) W. L. Leong and J. J. Vittal, Chem. Rev., 2011, 111, 688; (b) J. J. Perry,
J. A. Perman and M. J. Zaworotko, Chem. Soc. Rev., 2009, 38, 1400;
(c) D. J. Tranchemontagne, J. L. Mendoza, M. O’Keeffe and O. M. Yaghi,
Chem. Soc. Rev., 2009, 38, 1257; (d) S. Kitagawa, R. Kitaura and S. Noro,
Angew. Chem., Int. Ed., 2004, 43, 2334; (e) C. N. R. Rao, S. Natarajan
and R. Vaidhyanathan, Angew. Chem., Int. Ed., 2004, 43, 1466;
(f) S. L. Qiu and G. S. Zhu, Coord. Chem. Rev., 2009, 253, 2891;
(g) S. R. Batten, CrystEngComm, 2001, 3, 67; (h) G. Aromi,
L. A. Barrios, O. Roubeau and P. Gamez, Coord. Chem. Rev., 2011, 255,
485; (i) S. Natarajan and P. Mahata, Chem. Soc. Rev., 2009, 38, 2304.
2 (a) L. J. Murray, M. Dinca and J. R. Long, Chem. Soc. Rev., 2009, 38,
1294; (b) A. M. Seayad and D. M. Antonelli, Adv. Mater., 2004, 16, 765;
(c) J. R. Li, R. J. Kuppler and H. C. Zhou, Chem. Soc. Rev., 2009, 38,
1477; (d) T. Dueren, Y. S. Bae and R. Q. Snurr, Chem. Soc. Rev., 2009, 38,
1237; (e) J. An and N. L. Rosi, J. Am. Chem. Soc., 2010, 132, 16;
(f) S. S. Kaye, A. Dailly, O. M. Yaghi and J. R. Long, J. Am. Chem. Soc.,
2007, 129, 14176; (g) A. J. Fletcher, K. M. Thomas and M. J. Rosseinsky,
J. Solid State Chem., 2005, 178, 2491; (h) M. Eddaoudi, J. Kim, N. Rosi,
D. Vodak, J. Wachter, M. O’Keeffe and O. M. Yaghi, Science, 2002, 295,
469.
3 (a) M. D. Allendorf, C. A. Bauer, R. K. Bhakta and R. J. T. Houk, Chem.
Soc. Rev., 2009, 38, 1330; (b) K. C. Stylianou, R. Heck, S. Y. Chong,
J. Bacsa, J. T. A. Jones, Y. Z. Khimyak, D. Bradshaw and
M. J. Rosseinsky, J. Am. Chem. Soc., 2010, 132, 4119; (c) D. F. Weng,
X. J. Zheng, L. C. Li, W. W. Yang and L. P. Jin, Dalton Trans., 2007,
4822; (d) A. Rodriguez-Dieguez, S. Galli, N. Masciocchi, J. M. Gutierrez-
Zorrilla, P. Vitoria and E. Colacio, Dalton Trans., 2007, 1821;
(e) J. W. Cheng, S. T. Zheng and G. Y. Yang, Dalton Trans., 2007, 4059;
(f) Y. Q. Sun, J. Zhang and G. Y. Yang, Chem. Commun., 2006, 4700;
(g) B. D. Chandler, D. T. Cramb and G. K. H. Shimizu, J. Am. Chem.
Soc., 2006, 128, 10403; (h) D. F. Sun, D. J. Collins, Y. X. Ke, J. L. Zuo
and H. C. Zhou, Chem.–Eur. J., 2006, 12, 3768; (i) Q. Hou, J. H. Yu,
J. N. Xu, Q. F. Yang and J. Q. Xu, CrystEngComm, 2009, 11, 2452;
( j) J. H. Yu, Z. L. Lü, J. Q. Xu, H. Y. Bie, J. Lu and X. Zhang, New
J. Chem., 2004, 28, 940.
4 (a) D. F. Weng, Z. M. Wang and S. Gao, Chem. Soc. Rev., 2011, 40, 3157;
(b) K. S. Murray, Aust. J. Chem., 2009, 62, 1081; (c) M. Kurmoo, Chem.
Soc. Rev., 2009, 38, 1353; (d) S. R. Batten and K. S. Murray, Coord.
Chem. Rev., 2003, 246, 103; (e) Y. G. Huang, F. L. Jiang and M. C. Hong,
Coord. Chem. Rev., 2009, 253, 2814.
5 (a) X. X. Hu, J. Q. Xu, P. Cheng, X. Y. Chen, X. B. Cui, J. F. Song,
G. D. Yang and T. G. Wang, Inorg. Chem., 2004, 43, 2261; (b) X. X. Hu,
C. L. Pan, J. Q. Xu, X. B. Cui, G. D. Yang and T. G. Wang, Eur. J. Inorg.
Chem., 2004, 1566; (c) B. Morzyk-Ociepa, J. Mol. Struct., 2007, 846, 74;
(d) B. Morzyk-Ociepa, J. Mol. Struct., 2007, 833, 121;
(e) D. R. Whitcomb and M. Rajeswaran, J. Chem. Crystallogr., 2006, 36,
587.
Conclusion
In summary, we reported the syntheses, structural characteriz-
ation and photoluminescence properties of four new monoacyl-
hydrazidate-coordinated compounds. Based on the syntheses and
structural information of the obtained compounds, several sig-
nificant conclusions could be drawn as below: (i) the monoacyl-
hydrazidate molecule could be synthesized by two kinds of
hydrothermal ligand in situ reactions; an acylation reaction
between an organopolycarboxylic acid and N2H4·H2O, and a
reduction reaction of NPTH with N2H4·H2O as the reducer. (ii)
The acylhydrazidate molecule is a kind of good bridging-type
ligand, which is due to the potential diversity of the coordination
modes. The hydroxylimino N and O atoms as well as the acyl-
amino O atom could all act as the donors to coordinate to the
metal centers, but the uncoordinated acylamino groups could
also be prone to form the hydrogen-bonded dimer, an interesting
synthon. (iii) In the complex, the monoacylhydrazidate molecule
shows a −1 oxidation state. (iv) In the complex, the acylhydrazi-
date molecule exists in the ketohydroxy form, and sometimes it
exists in the diketo form. (v) The geometric configuration of the
metal center and the substituting group on the acylhydrazidate
molecule have effects on the network structures of the obtained
products. (vi) The photoluminescence analysis for the title com-
pounds further confirms that the acylhydrazidate-coordinated
complex is really the potential photoluminescence material. The
DFT calculations were applied to better understand the emission
mechanism of the compounds. Two kinds of new charge-transfer
paths are found in acylhydrazidate-coordinated compounds.
6 (a) J. Jin, F. Q. Bai, M. J. Jia, Y. Peng, J. H. Yu and J. Q. Xu, Dalton
Trans., 2012, 41, 2382; (b) J. H. Yu, Y. C. Zhu, D. Wu, Y. Yu, Q. Hou and
J. Q. Xu, Dalton Trans., 2009, 8248; (c) J. Jin, M. J. Jia, Y. Peng, Q. Hou,
J. H. Yu and J. Q. Xu, CrystEngComm, 2010, 12, 1850; (d) J. Jin, D. Wu,
M. J. Jia, Y. Peng, J. H. Yu, Y. C. Wang and J. Q. Xu, J. Solid State
Chem., 2011, 184, 667; (e) J. Jin, W. Xu, M. J. Jia, J. J. Zhao, J. H. Yu and
J. Q. Xu, Inorg. Chim. Acta, 2011, 378, 72; (f) J. Jin, M. J. Jia, J. J. Zhao,
J. H. Yu and J. Q. Xu, J. Cluster Sci., DOI: 10.1007/s10876-011-0428-9.
7 G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr., 2008, 64,
112.
8 P. Diaz, J. Benet-Buchholz, R. Vilar and A. J. P. White, Inorg. Chem.,
2006, 45, 1617.
This journal is © The Royal Society of Chemistry 2012
Dalton Trans., 2012, 41, 6137–6147 | 6147