rapidly stirred at 30 ◦C. After 5 min, L-lactide (2.88 g, 20.0 mmol)
in CH2Cl2 (7 mL) were added to the activated species, and the
reaction mixture was stirred at 30 ◦C for 3 h. The conversion
yield (99%) of PLLA-200 was analyzed by 1H NMR spectroscopic
analysis. After the reaction was quenched by the addition of excess
water (0.5 mL), the polymer was precipitated into hexane (100
mL). The final polymer was then dissolved in THF (20 mL) and
purified upon precipitation again in MeOH (150 mL), collected
and dried under vacuum. Yield: 2.76 g (96%).
Dalton Trans., 2003, 3799–3803; (e) C.-T. Chen, C.-A. Huang and B.-H.
Huang, Macromolecules, 2004, 37, 7968–7973; (f) L. E. Breyfogle, C.
K. Williams, V. G. Jr. Young, M. A. Hillmyer and W. B. Tolman, Dalton
Trans., 2006, 928–936; (g) A. Amgoune, C. M. Thomas, S. Ilinca, T.
Roisnel and J.-F. Carpentier, Angew. Chem., Int. Ed., 2006, 45, 2782–
2784; (h) J. Ejfler, S Szafert, K. Mierzwicki, L. B. Jerzykiewicz and P.
Sobota, Dalton Trans., 2008, 6556–6562; (i) C.-A. Huang, C.-L. Ho and
C.-T. Chen, Dalton Trans., 2008, 3502–3510; (j) N. Ajellal, M. Bouyahyi,
A. Amgoune, C. M. Thomas, A. Bondon, I. Pillin, Y. Grohens and J.-
F. Carpentier, Macromolecules, 2009, 42, 987–993; (k) V. Poirier, T.
Roisnel, J.-F. Carpentier and Y. Sarazin, Dalton Trans., 2009, 9820–
9827; (l) G. Labourdette, D. J. Lee, B. O. Patrick, M. B. Ezhova and P.
Mehrkhodavandi, Organometallics, 2009, 28, 1309–1319.
4 (a) H.-Y. Chen, H.-Y. Tang and C.-C. Lin, Macromolecules, 2006, 39,
3745–3752; (b) W.-C. Hung, Y. Huang and C.-C. Lin, J. Polym. Sci.,
Part A: Polym. Chem., 2008, 46, 6466–6476; (c) W.-C. Hung and C.-C.
Lin, Inorg. Chem., 2009, 48, 728–734.
5 (a) C.-Y. Li, C.-Y. Tsai, C.-H. Lin and B.-T. Ko, Dalton Trans., 2011,
1880–1887; (b) Y.-E. Tai, C.-Y. Li, C.-H. Lin, Y.-C. Liu, B.-T. Ko and
Y.-S. Sun, J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 4027–4036.
6 (a) J.-Y. Li, Y.-C. Liu, C.-H. Lin and B.-T. Ko, Acta Crystallogr., Sect.
E: Struct. Rep. Online, 2009, E65, o2475; (b) C.-H. Li, J.-K. Su, C.-Y.
Li and B.-T. Ko, Acta Crystallogr., Sect. E: Struct. Rep. Online, 2010,
E66, o2825.
X-ray crystallographic studies
Suitable crystals of complex 1–4 were mounted onto glass fiber
using perfluoropolyether oil and cooled rapidly in a stream
of cold nitrogen gas to collect diffraction data at 173 K or
100 K using Bruker APEX2 diffractometer. Intensity data were
collected in 1350 frames with increasing w (width of 0.5◦ per
frame). The absorption correction was based on the symmetry-
equivalent reflections using SADABS program.16 The space group
determination was based on a check of the Laue symmetry
and systematic absence, and was confirmed using the structure
solution. The structures were solved with direct methods using
a SHELXTL package.17 All non-H atoms were located from
successive Fourier maps, and hydrogen atoms were refined using
a riding model. Anisotropic thermal parameters were used for all
non-H atoms, and fixed isotropic parameters were used for H-
atoms. Crystallographic data of complexes 1–4 are summarized in
Table 3.
7 J.-Y. Li, C.-Y. Li, W.-J. Tai, C.-H. Lin and B.-T. Ko, Inorg. Chem.
Commun., 2011, 14, 1140–1144.
8 J. Rosevear and J. F. K. Wilshire, Aust. J. Chem., 1985, 38, 1163–1176.
9 J. Lee, S. H. Kim, K. M. Lee, K. Y. Hwang, H. Kim, J. O. Huh, D. J.
Kim, Y. S. Lee, Y. Do and Y. Kim, Organometallics, 2010, 29, 347–353.
10 (a) W. Y. Yang, H. Schmider, Q. D. Wu, Y. S. Zhang and S. Wang,
Inorg. Chem., 2000, 39, 2397–2404; (b) Q. G. Wu, J. A. Lavigue, Y. Tao,
M. D’Iorio and S. Wang, Inorg. Chem., 2000, 39, 5248–5254; (c) X.
Liu, W. Gao, Y. Mu, G.-H. Li, L. Ye, H. Xia, Y. Ren and S.-H. Feng,
Organometallics, 2005, 24, 1614–1619; (d) Q. Su, W. Gao, Q.-L. Wu, L.
Ye, G.-H. Li and Y. Mu, Eur. J. Inorg. Chem., 2007, 4168–4175.
11 (a) D. Rendell, (Ed.), Fluorescence and Phosphorescence, Wiley, New
York, 1987; (b) H. Yersin, A. Vogler, (ed.), (Photochemistry and
Photophysics of Coordination Compounds, Springer, Berlin, 1987;
(c) A. W. Adamson, P. D. Fleischauer, (ed.), (Concepts of Inorganic
Photochemistry, Wiley, New York, 1975; (d) N. I. Nijegorodov and W.
S. Downey, J. Phys. Chem., 1994, 98, 5639–5643.
Acknowledgements
We gratefully acknowledge financial support from the National
Science Council, Taiwan (NSC99-2113-M-033-007-MY2). We
also thank Professor Pi-Tai Chou and Dr Ching-Yen Wei for
valuable discussions of PL quantitative characterization.
12 (a) C.-Y. Tsai, C.-Y. Li, C.-H. Lin, B.-H. Huang and B.-T. Ko, Inorg.
Chem. Commun., 2011, 14, 271–275; (b) C.-H. Wang, C.-Y. Li, C.-H.
Lin, Y.-C. Liu and B.-T. Ko, Inorg. Chem. Commun., 2011, 14, 1456–
1460.
13 (a) H. Tsujit and Y. Ikada, Macromolecules, 1993, 26, 6918–6926; (b) R.
T. MacDonald, S. P. McCarthy and R. A. Gross, Macromolecules, 1996,
29, 7356–7361; (c) J. Huang, M. S. Lisowski, J. Runt, E. S. Hall, R. T.
Kean, N. Buehler and J. S. Lin, Macromolecules, 1998, 31, 2593–2599;
(d) J. R. Sarasua, R. E. Prud’homme, M. Wisniewski, A. L. Borgne and
N. Spassky, Macromolecules, 1998, 31, 3895–2905; (e) R. E. Drumright,
P. R. Gruber and D. E. Henton, Adv. Mater., 2000, 12, 1841–1846.
14 (a) J.-C. Wu, B.-H. Huang, M.-L. Hsueh, S.-L. Lai and C.-C. Lin,
Polymer, 2005, 46, 9784–9792; (b) Y. Huang, W.-C. Hung, M.-Y. Liao,
T.-E. Tsai, Y.-L. Peng and C.-C. Lin, J. Polym. Sci., Part A: Polym.
Chem., 2008, 46, 6466–647.
15 (a) J. Baran, A. Duda, A. Kowalski, R. Szymanski and S. Penczek,
Macromol. Rapid Commun., 1997, 18, 325–333The Mn (GPC) value is
multiplied by a factor of 0.58, giving the actual Mn of the polylactide,
see: (b) T. Biela, A. Duda and S. Penczek, Macromol. Symp., 2002, 183,
1–10.
References
1 (a) B. J. O’Keefe, M. A. Hillmyer and W. B. Tolman, J. Chem. Soc.,
Dalton Trans., 2001, 2215–2224; (b) A. C. Albertsson and I. K. Varma,
Biomacromolecules, 2003, 4, 1466–1486; (c) O. Dechy-Cabaret, B.
Martin-Vaca and D. Bourissou, Chem. Rev., 2004, 104, 6147–6176;
(d) J. Wu, T.-L. Yu, C.-T. Chen and C.-C. Lin, Coord. Chem. Rev., 2006,
250, 602–626; (e) C. A. Wheaton, P. G. Hayes and B. J. Ireland, Dalton
Trans., 2009, 4832–4846.
2 (a) W. Gao, D. Cui, X. Liu, Y. Zhang and Y. Mu, Organometallics, 2008,
27, 5889–5893; (b) W. Yao, Y. Mu, A. Gao, W. Gao and L. Ye, Dalton
Trans., 2008, 3199–3206; (c) Y.-H. Tsai, C.-H. Lin, C.-C. Lin and B.-T.
Ko, J. Polym. Sci., Part A: Polym. Chem., 2009, 47, 4927–4936; (d) Y.-C.
Liu, C.-H. Lin, B.-T. Ko and R.-M. Ho, J. Polym. Sci., Part A: Polym.
Chem., 2010, 48, 5339–5347.
3 (a) C. K. Williams, N. R. Brooks, M. A. Hillmyer and W. B. Tolman,
Chem. Commun., 2002, 2132–2133; (b) C. K. Williams, L. E. Breyfogle,
S. K. Choi, W. Nam, V. G. Jr. Young, M. A. Hillmyer and W. B.
Tolman, J. Am. Chem. Soc., 2003, 125, 11350–11359; (c) L. M. Alcazar-
Roman, B. J. O’Keefe, M. A. Hillmyer and W. B. Tolman, Dalton
Trans., 2003, 3082–3087; (d) C.-T. Chen, C.-A. Huang and B.-H Huang,
16 G. M. Sheldrick, SADABS, Program for area detector absorption
correction, Institute for Inorganic Chemistry, University of Go¨ttingen,
Germany, 1996.
17 G. M. Sheldrick, SHELXTL-97, Program for refinement of crystal
structures, University of Go¨ttingen, Germany, 1997.
This journal is
The Royal Society of Chemistry 2012
Dalton Trans., 2012, 41, 953–961 | 961
©