Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 0 Supporting Information A rare three-coordinated zinc cluster-organic framework with two types of second building units Jin-Song Hu, a, b Lei Zhang, b Ling Qin, a He-Gen Zheng,*,a Xiang-Biao Zhang*,b a State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 00, P. R. China. b School of Chemical Engineering, Anhui University of Science and Technology, Huainan 00. Materials and methods. Synthesis procedure. Electronic structure calculations. CD, PXRD, TGA and luminescent and the photoluminescence lifetime patterns. Bond Lengths (Å) and Angles (deg) of
. Materials and methods Reagents and solvents employed were commercially available and used as received. Ligand H NTB was prepared by the literature methods [S]. IR absorption spectra of the complexes were recorded in the range of 00 000 cm - on a Nicolet (Impact 0) spectrometer with KBr pellets ( mg of sample in 00 mg of KBr). Powder X-ray diffraction (PXRD) measurements were performed on a Bruker D Advance X-ray diffractometer using Cu-Kα radiation (0. nm), in which the X-ray tube was operated at 0 kv and 0 ma. Luminescent spectra were recorded with a SHIMAZU VF 0 X-ray fluorescence spectrophotometer at room temperature. The photoluminescence lifetime was measured with an Edinburgh Instruments FLS0P fluorescence spectrometer. The as-synthesized samples were characterized by thermogravimetric analysis (TGA) on a Perkin Elmer thermogravimetric analyzer Pyris TGA up to 0 K using a heating rate of 0 K min - under N atmosphere. A pulsed Q-switched Nd:YAG laser at a wavelength of 0 nm was used to generate a SHG signal. The backscattered SHG light was collected by a spherical concave mirror and passed through a filter that transmits only nm radiation. The solvent molecules in the structure were found to be highly disordered and were impossible to refine using conventional discrete-atom models. To resolve these issues, the contribution of the electron density by the remaining solvent molecules was removed by the SQUEEZE routine in PLATN [S]. The numbers of solvent molecules were obtained by element analysis, IR and TGA. References [S] J. Wang, C. He, P. Y. Wu, J. Wang, C. Y. Duan, J. Am. Chem. Soc., 0,, 0. [S] A. L. Spek, Acta Crystallogr., Sect. A: Found Crystallogr. 0,,.
. Synthesis procedure A mixture of (N ) H (0. mmol), H NTB (0. mmol) and H NDB (0. mmol) is dispersed in 0 ml H, and the mixture is adjusted to ph=. The final mixture is placed in a Parr Teflon-lined stainless steel vessel ( ml) and heated at 0 C for d. Large quantities of faint yellow-block crystals is obtained, the crystals are filtered off, washed with mother liquid, and dried under ambient conditions. yield of the reaction is ~0%. Anal. Calcd for C H N : C, 0.%, H,.%, N,.%; found C, 0.%, H,.%, N,.%. IR (KBr, cm - ): (w), (w), (m), (s), 0(s), (s), (s), (w), (m), 0(m), 00(w), (w), (m), (s), (m).. Electronic structure calculations Computational details Starting from the crystal structures, geometry optimizations were performed for clusters H (μ -)(C) and H (μ -) (C) using the DFT/BLYP/ - G(d) with diffuse functions for oxygen atoms. In order to obtain the same geometry configurations with clusters in the MFs, H (μ -)(C) and H (μ - ) (C) are constrainted to have C and D symmetries, respectively. To further study the configuration of H (μ -) (C), we calculated its structure again without any symmetry constraint. As a result, a stable configuration H (μ -)(μ - ) (C) was obtained. Based on the optimized geometry structures, frequency calculations were carried out at the same theoretical level and accurate electronic energies for these clusters were calculated using the DFT/BLYP/-++G(d,p). Finally, we performed natural bond orbital (NB) analysis[s] for all the clusters. All the calculations were carried out with the Gaussian0 package[s]. ur calculation methods have been successfully used to the similar study of the clusters.[s] The calculated results indicate that H (μ -)(C) and H (μ -)(μ -) (C) have no imaginary frequency and H (μ -) (C) has five imaginary frequencies (-.i, -.i, -.0i, -.0i, -.i).
Cartesian coordiantes and electronic energies (E) by the BLYP/ -++G(d,p) H (μ -)(C) (E = -. au) Center Number Atomic Number Coordinates (Angstroms) 0 0 X Y Z -0. -0. -0. -0.0-0.0-0.0....... 0. 0. 0...0.0.0.0.0.0-0. -.0-0. -.0-0. -.0 0.0-0.000.. -.. -.0..0-0.0.0..00-0....00....00 -. -.0...0. -.00 -.0 0.00.0.0-0.0.00.0.00. 0...00.00....0..00. 0. 0.. 0. -0. -...00.0. H (μ -) (C) (E = -.0 au)
Coordinates (Angstroms) Center Number Atomic Number X Y Z 0 0 0 -.0 -.0 -.0.0 0.. -.. 0.0 -..0-0.0. -.0 -.0.0.0-0.0.0 -.0 -. -. -. -. 0.0.....0-0. -..0... 0.0. 0..0.0.0 -.. -0. -0....0.. -0. -. -. -0. -. 0. 0. -. -0. -.0 -. -. -.0 -. -. -0. 0. -.. -. -.00 -. -. -....0 0.0-0.0... -0.00 -. -. 0.00-0.0 0.0-0.0 0.0.. -. -. 0.00. -0.00 -. -. 0.00. -0.00 -. -.0 -. -. -.0 -.0.0.0 -.0
0 0-0... -.000 -.0 -. -. -.0 -. -. -. -0.0 0..000.0.. -. -. -.0..0.. -. -. -. -.00..0 -. -.0....00..00 -.0 -.0 -.0 -.0 -.0 -.0 -.0.0.0.0.0.0.0.0.0.0.0 -.0 -.0 H (μ -)(μ -) (C) (E = -.00 au) Coordinates (Angstroms) Center Number Atomic Number X Y Z 0 0-0.0.. 0.0 0..0 -. 0. -..0 -. 0.. -.0 -.0 -..00.0 -. -..... -0...0 0..0 -. -.0.. 0..0.0 -. -.000 -. -0. 0.00 -. -0.00 -. -0. 0. 0.0 -.00 -. -0.0-0.0 0.... 0.00.0 -.0 -.0-0.
0 0 0. -.0..0...0-0. -.0 -.0 -. -.0 -.00 -. -. 0. -. -. -. -.0 -.00-0.00 -. -. 0. 0.0..0..0.00.0.0.00 -. -. -.0 -.0 0. 0. -0.0. -.0 -.0 0. 0. -. -.0 -. -.0-0.0 -. -0. -.0 -.0 -.00 -. -.0 -. -. -.0 -. 0.0 0. -.0 -. -.0 -. 0.0.0.. -0.0 0..0.0..0.. -.0 -.. 0.. -0. -. -0.0-0. -. -. -0.0.0..0. -0.0-0. -. -.00....00.0. -0. -0. 0. 0.00 -. -.0 -. -.00 -. -.0 0. 0...0 Summary of natural population analyses
Center Natural Natural Population Atom Number Charge Cor Val Ryd Total H (μ -)(C) 0-0. -0. -0. -0.0-0.0-0.0-0. -0. -0.0-0. -0. -0. -....0.0......................0........ 0.00 0.00 0.00 0.0 0.0 0.0 0.0 0.00 0.00 0.00 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00 0.0 0.0 0.0....0.0.0...0.....0.0.. 0 Natural Electron Configuration [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) H (μ -) (C)
0 0 -. -0. -0..0.0.. -0. -0. -. -. -0. -0. -0. -0. -0..... -0. -0. -0. -0. -0. -0. -0. -0. -0. -0. -0. -0. -0..0-0. -0....0...........0.......0.0.0.....0..........0.0 0.0 0. 0. 0..0.0....0.0..0 0. 0. 0. 0..0.0.0..0..0.0..0..0.0 0.0.0.0 0.000 0.0 0.00 0.0 0.00 0.000 0.000 0.0 0.0 0.000 0.000 0.0 0.0 0.00 0.0 0.0 0.000 0.000 0.000 0.000 0.00 0.00 0.00 0.0 0.0 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0....0.0.............................0.. Natural Electron Configuration [core]s(.)p(.)p( 0.0)p( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0)
0 0 [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) H (μ -)(μ -) (C) 0 -.0-0. -0...0.0. -0. -0. -.....0..0.....00.. 0. 0. 0.0 0...00. 0.0000 0.00 0.0 0.00 0.0 0.0 0.0 0.0 0.0 0.0.0......... 0
0 -. -0. -0. -0. -0. -0.0..0.. -0.00-0. -0.00-0.0-0. -0.0-0. -0. -0.0-0.0-0. -0. -0.. -0. -0..........0.00..............0......0.. 0.0 0.00 0.0 0...0...00.0.0.0.....0 0... 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.00 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0......0..0...00..00.0..0...0.0...... 0 Natural Electron Configuration [core]s(.)p(.)p( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)S( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s(.)p(.0)s( 0.0)p( 0.0)d( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0) [core]s(.)p(.)p( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0)
0 [core]s(.)p(.)p( 0.0)d( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s( 0.)d(.)p( 0.0) [core]s( 0.)d(.)p( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.0)p( 0.0)d( 0.0) [core]s( 0.)d(.)p( 0.0)p( 0.0) [core]s(.)p(.)p( 0.0)d( 0.0) [core]s(.)p(.)s( 0.0)p( 0.0)d( 0.0) References [S] E. D. Glendening, A. E. Reed, J. E. Carpenter and F. Weinhold, NB Version.. [S] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. chterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain,. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. rtiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong,
C. Gonzalez and J. A. Pople, GAUSSIAN 0 (Revision D.0), Gaussian, Inc., Wallingford CT, 00. [S] (a) D. Samanta and P. Jena, J. Am. Chem. Soc., 0,, 00; (b) S. S. Hepperle and Y. A. Wang, J. Phys. Chem. A, 0,, ; (c) D. P. Martin, P. G. Blachly, A. R. Marts, T. M. Woodruff, C. A. F. de liveira, J. A. McCammon, D. L. Tierney and S. M. Cohen, J. Am. Chem. Soc., 0,, 00.
. CD, PXRD, TGA and luminescent and the photoluminescence lifetime patterns CD/mdeg 0 Complex - 00 0 00 00 00 Wavelength/nm Figure S. Solid-state circular dichroism spectrum of exprimental simulated 0 0 0 0 degree( ) Figure S. Powder X-ray diffraction pattern of Figure S. The TGA pattern of complex
Figure S. The solid photoluminescent patterns of complex, H NTB and H NDB a b Figure S. The fitted decay curve monitored at 0nm (a) and 0 nm (b) for complex in the solid state at room temperature. The sample is excited at 0 nm. Yellow lines: experimental data; Solid line: fitted by Fit = A+B exp(-t/τ )+B exp(- t/τ ).
. Bond lengths (Å) and angles (deg) of complex Table S. Selected Bond Lengths (Å) and Angles (deg) for Complex Complex -.0() -.() -.() -.() -.() -.() -.0() -.0() -.() -.() 0-.() 0-.0() --.() -- 0.0 -#-.0() -#-.() -# 0.() -#-.0() -#-.() -#- 00.() --.() -- 0.() -- 0.() --0 0.() --0.() --0 0.() 0-- 0.() -- 0.0() # = -x, -x+y, -z.