經由不斷的嘗試，在 H2bpyany 配基上做修飾，合成了許多不同 修飾的配基，最後在 H2bphpyany、H2bphpmany、H2bphpzany 這三個 配基有良好的收穫，因此我的研究主要就是以這三個配基來合成鎳金 屬串與鈷金屬串兩個部分。
在鎳金屬串的部分，我們成功合成 [Ni6(bphpyany)4Cl2](PF6)2 (1)、
[Ni6(bphpyany)4Cl2](PF6) (2) 、 [Ni6(bphpyany)4(NCS)2](PF6)2 (3) 、 [Ni6(bphpmany)4Cl2](PF6)2 (4) 、[Ni6(bphpmany)4Cl2](PF6) (5)等五個化 合物並且在化合物 1-4 有得到其單晶結構。在結構方面，經過單晶繞 射解析後，與[Ni6(bpyany)4Cl2](PF6)2、[Ni6(bpyany)4Cl2](PF6)比較，可 以發現相關鍵長並沒有明顯的變化。在磁性方面，與結構的預測相符，
末端五配位的 Ni2+屬於高自旋(S = 1)，其餘中間四配位的 Ni2+為低自 旋(S = 0)，化合物 2 還原 1 個電子在中間萘啶單元的 Ni2單元上，因 此 S34 = 1/2，化合物 5 還原 1 個電子在中間萘啶單元的 Ni2單元上，
從在 300 K 時的 μeff值來推測，中間萘啶單元的 Ni23+有可能為 S34 = 3/2，
因此這部分還需要做更多的鑑定才有辦法確認。化合物 1、2、4 經由 公式擬合後，得到的 coupling coefficient (J)分別為-4.2、-54、-4.57 cm-1， 與已發表的六核鎳金屬串相似。且我們整理了已發表的多核鎳金屬串
129
的 coupling coefficient (J)與兩端 high spin 的 Ni 距離 (r)，從公式的推 導可以得知，其-J 與 r-3成正比關係，得到一良好的線性關係圖，且 化 合 物 1、 4 都在 其 線 性上 。在電 化 學 的研 究，1 與 文 獻 中 的 [Ni6(bpyany)4Cl2](PF6)2電化學表現相似，而 4 則是有一點差異，且圖 形並不是很好，需要重新做確認。
在 鈷 金 屬 串 的 部 分 ， 成 功 合 成 並 且 具 有 單 晶 結 構 的 有 [Co6(bphpyany)4(NCS)2](PF6) (6)、[Co6(bphpyany)4(NCS)2](PF6)2 (7)、
[Co5(bphpzany)4(NCS)2] (8) 、 [Co5(bphpzany)4(OTf)2] (9) 、 [Co6(bphpzany)4(NCS)2](PF6) (10)等五個化合物。六核鈷金屬串有 6、
7、 10 三個 化合物， 結構與已 發表的 [Co6(bpyany)4(NCS)2](PF6)、
[Co6(bpyany)4(NCS)2](PF6)2比對，其鍵長也是相類似，沒有明顯的變 化。磁性方面，6、10 為 Spin-crossover process (S = 1/2 ⇆ S = 3/2)的 表現，不同於[Co6(bpyany)4(NCS)2](PF6)是 S = 1/2 的順磁性，可以推 測修飾上苯基後，降低原有的 LUMO 軌域，使其產生 SCO 的現象。
而氧化 1 個電子的 7，則與[Co6(bpyany)4(NCS)2](PF6)2相同，為 S = 1。
電化學研究顯示，修飾上苯基後，不會有明顯的改變。而用 pyrazine 取代 pyridine 後，第一個還原電位可以降低 410 mV，是目前六核鈷 金屬串的研究中，最能有效降低還原電位的配基修飾。在 defective 五 核 鈷 金 屬 串 的 部 分 ， 8 、 9 的 相 關 鍵 長 與 文 獻 中 的
130
[Co5(bpzany)4(NCS)2]相似，磁性的表現與電化學的研究，都與文獻大 致相同。最後導電度的研究，修飾苯基後的導電度介於未修飾的 [Co6(bpyany)4(NCS)2]+和修飾甲基的[Co6(bmpyany)4(NCS)2]+之間，而 以 pyrazine 取代 pyridine 可以再微微改善其導電度。將 fully delocalized 10 與 defective 8 比較，發現導電值相差無幾。我們利用理論計算，
分析其主要導電的分子軌域，可以發現化合物 8 與 10 的該軌域 bond order 分布相似，因此可以解釋巨觀時的缺陷，卻沒有導致電阻值上 升的主要原因。第二個部分導電度的研究，顯示化合物 6+、10+與氧 化後 62+、102+導電值相當，我們用 bond order 來解釋其現象，因為氧 化一個電子後，bond order 從 0.4 僅僅上升至 0.5，因此導電值不會因 為氧化一個電子後而有顯著的改變。
在第二章節有提到未養晶或純化成功的化合物有不少，未來可以 試著將那些化合物純化，測量其磁性、電化學、導電度等等，來使六 核鎳金屬串與鈷金屬串有更完整的研究。
131
參考文獻
1. A. Aviram and M. Ratner, Chem. Phys. Lett., 1974, 29, 277–283.
2. S.-A. Hua, M.-C. Cheng, C.-h. Chen and S.-M. Peng, Eur. J. Inorg.
Chem., 2015, 2510–2523.
3. K. Krogmann, Angew. Chem. infernat. Edit., 1969, 8, 35–42.
4. (a) V. M. Miskowski, I. S. Sigal, K. R. Mann, H. B. Gary, S. J. Milder, G. S. Hammond and P. R. Ryason, J. Am. Chem. Soc., 1979, 101, 4383–4385. (b) I. S. Sigal, K. R. Mann and H. B. Gary, J. Am. Chem.
Soc., 1980, 102, 7252–7256. (c) J. K. Barton, S. A. Best, S. J.
Lippard and R. A. Walton, J. Am. Chem. Soc., 1978, 100, 3785–3788.
(d) C. Tejel, M. A. Ciriano, J. A. López, F. J. Lahoz and L. A. Oro, Angew. Chem. Int. Ed., 1998, 37, 1542–1545. (e) C. Tejel, M.
Sommovigo, M. A. Ciriano, J. A. López, F. J. Lahoz and L. A. Oro, Angew. Chem. Int. Ed., 2000, 39, 2336–2339. (f) C. Tejel, M. A.
Ciriano, B. E. Villarroya, R. Gelpi, J. A. López, F. J. Lahoz and L. A.
Oro, Angew. Chem. Int. Ed., 2001, 40, 4084–4086. (g) M. E. Prater, L.
E. Pence, R. Clerac, G. M. Finniss, C. Campana, D. Jerome, P.
Auban-Senzier, E. Canadell and K. R. Dunbar, J. Am. Chem. Soc., 1999, 121, 8005–8016.
5. (a) F. A. Cotton, N. F. Curtis, C. B. Harris, B. F. G. Johnson, S. J.
Lippard, J. T. Mague, W. R. Robinson and J. S. Wood, Science, 1964, 145, 1305–1307. (b) F. A. Cotton, N. F. Curtis, B. G. Johnson and W.
R. Robinson, Inorg. Chem., 1965, 4, 326–330. (c) F. A. Cotton and C.
B. Harris, Inorg. Chem., 1965, 4, 330–333.
132
6. (a) S. Ogoshi, K. Tsutsumi, M. Ooi and H. Kurosawa, J. Am. Chem.
Soc., 1995, 117, 10415–10416. (b) T. Murahashi, E. Mochizuki, Y.
Kai and H. Kurosawa, J. Am. Chem. Soc., 1999, 121, 10660–10661.
(c) T. Murahashi, Y. Higuchi, T. Katoh and H. Kurosawa, J. Am.
Chem. Soc., 2002, 124, 14288–14289. (d) T. Murahashi, T. Uemura and H. Kurosawa, J. Am Chem. Soc., 2003, 125, 8436–8437. (e) T.
Murahashi, M. Fujimoto, Y. Kawabata, R. Inoue, S. Ogoshi and H.
Kurosawa, Angew. Chem. Int. Ed., 2007, 46, 5440–5443.
7. (a) K. Mashima, H. Nakano and A. Nakamura, J. Am. Chem. Soc., 1993, 115, 11632–11633. (b) K. Mashima, H. Nakano and A.
Nakamura, Inorg. Chem., 1996, 35, 4007–4012. (c) K. Mashima, M.
Tanaka, K. Tani, H. Nakano and A. Nakamura, Inorg. Chem., 1996, 35, 5244–5248. (d) T. Rüffer, M. Ohashi, A. Shima, H. Mizomoto, Y.
Kaneda and K. Mashima, J. Am. Chem. Soc., 2004, 126, 12244–
12245. (e) M. Ohashi, A. Shima, T. Rüffer, H. Mizomoto, Y. Kaneda and K. Mashima, Inorg. Chem., 2007, 46, 6702–6714.
8. M.-J. Huang, S.-A. Hua, M.-D. Fu, G.-C. Huang, C.-X. Yin, C.-H.
Ko, C.-K. Kuo, C.-H. Hsu, G.-H. Lee, K.-Y. Ho, C.-H. Wang, Y.-W.
Yang, I-C. Chen, S.-M. Peng and C.-h. Chen, Chem. Eur. J., 2014, 20, 4526–4531.
9. J. P. Wibaut and E. Dingemasse, Rec. Trav. Chim. Pays-Bas, 1923, 42, 240–250.
10. S. Wagan and S. L. Buchwald, J. Org. Chem., 1996, 61, 7240–7241.
11. (a) R. Clerac, F. A. Cotton, L. M. Daniels, K. R. Dunbar, K.
Kirschbaum, C. A. Murillo, A. A. Pinkerton, A. J. Schultz and X. P.
133
Wang, J. Am. Chem. Soc., 2000, 122, 6226–6236. (b) J.-T. Sheu, C.-C.
Lin, I Chao, C.-C. Wang and S.-M. Peng, Chem. Commun., 1996, 32, 315–316. (c) J. F. Berry, F. A. Cotton, L. M. Daniels, C. A. Murillo and X. Wang, Inorg. Chem., 2003, 42, 2418–2427. (d)I-W. P. Chen, M.-D. Fu, W.-H. Tseng, J.-Y. Yu, S.-H. Wu, C.-J. Ku, C.-h. Chen and S.-M. Peng, Angew. Chem. Int. Ed., 2006, 45, 5814–5818. (e) M.-C.
Cheng, I. P.-C. Liu, C.-H. Hsu, G.-H. Lee, C.-h. Chen and S.-M.
Peng, Dalton Trans., 2012, 41, 3166–3173.
12. (a) W.-Z. Wang, R. H. Ismayilov, R.-R. Wang, Y.-L. Huang, C.-Y.
Yeh, G.-H. Lee and S.-M. Peng, Dalton Trans., 2008, 37, 6808–6816.
(b) S.-J. Shieh, C.-C. Chou, G.-H. Lee, C.-C. Wang and S.-M. Peng, Angew. Chem. Int. Ed., 1997, 36, 56–59. (c) H.-C. Chang, J.-T. Li, C.-C. Wang, T.-W. Lin, H.-C. Lee, G.-H. Lee and S.-M. Peng, Eur. J.
Inorg. Chem., 1999, 1243–1251.
13. (a) W.-Z. Wang, R. H. Ismayilov, G.-H. Lee, I. P.-C. Liu, C.-Y. Yeh and S.-M. Peng, Dalton Trans., 2007, 36, 830–839. (b) Y.-H. Chen, C.-C. Lee, C.-C. Wang, G.-H. Lee, S.-Y. Lai, F.-Y. Li, C.-Y. Mou and S.-M. Peng, Chem. Commun., 1999, 35, 1667–1668. (c) S.-Y. Lai, T.-W. Lin, Y.-H. Chen, C.-C. Wang, G.-H. Lee, M.-H. Yang, M.-K.
Leung and S.-M. Peng, J. Am. Chem. Soc., 1999, 121, 250–251.
14. S.-M. Peng, C.-C. Wang, Y.-L. Jang, Y.-H. Chen, F.-Y. Li, C.-Y.
Mou and M.-K. Leung, J. Magn. Magn. Mater., 2000, 209, 80–83.
15. F. A. Cotton, C. A. Murillo and Q. Wang, Inorg. Chim. Acta, 2010, 363, 4175–4180.
16. L. Sacconi, C. Mealli and D. Gatteschi, Inorg. Chem., 1974, 13,
134
1985–1991.
17. (a) I. P.-C. Liu, M. Bénard, H. Hasanov, I-W. P. Chen, W.-H. Tseng, M.-D. Fu, M.-M. Rohmer, C.-h. Chen, G.-H. Lee and S.-M. Peng, Chem. Eur. J., 2007, 13, 8667–8677. (b)H. Hasan, U.-K. Tan, G.-H.
Lee and S.-M. Peng, Inorg. Chem. Commun., 2007, 10, 983–988. (c) R. H. Ismayilov, W.-Z. Wang, G.-H. Lee, C.-Y. Yeh, S.-A. Hua, Y.
Song, M.-M. Rohmer, M. Bénard and S.-M. Peng, Angew. Chem. Int.
Ed., 2011, 50, 2045–2048.
18. (a) C.-H. Chien, J.-C. Chang, C.-Y. Yeh, G.-H. Lee, J.-M. Fang and S.-M. Peng, Dalton Trans., 2006, 35, 2106–2113. (b) C.-H. Chien, J.-C. Chang, C.-Y. Yeh, G.-H. Lee, J.-M. Fang, Y. Song and S.-M.
Peng, Dalton Trans., 2006, 35, 3249–3256. (c)S.-A. Hua, I. P.-C. Liu, H. Hasanov, G.-C. Huang, R. H. Ismayilov, C.-L. Chiu, C.-Y. Yeh, G.-H. Lee and S.-M. Peng, Dalton Trans., 2010, 39, 3890–3896.
19. (a) J. F. Berry, F. A. Cotton, T. Lu, C. A. Murillo and X. Wang, Inorg.
Chem., 2003, 42, 3595–3601. (b)J. F. Berry, F. A. Cotton, T. Lu and C. A. Murillo, Inorg. Chem., 2003, 42, 4425–4430. (c)J. F. Berry, F.
A. Cotton, P. Lei, T. Lu and C. A. Murillo, Inorg. Chem., 2003, 42, 3534–3539. (d) J. F. Berry, F. A. Cotton, C. S. Fewox, T. Lu, C. A.
Murillo and X. Wang, Dalton Trans., 2004, 33, 2297–2302. (e)C.-X.
Yin, J. Su, F.-J. Huo, R. H. Ismayilov, W.-Z. Wang, G.-H. Lee, C.-Y.
Yeh and S.-M. Peng, J. Coord. Chem., 2009, 62, 2974–2982.
20. (a) X. López, M.-Y. Huang, G.-C. Huang, S.-M. Peng, F.-Y. Li, M.
Bénard and M.-M. Rohmer, Inorg. Chem., 2006, 45, 9075–9084. (b)I.
P.-C. Liu, C.-F. Chen, S.-A. Hua, C.-H. Chen, H.-T. Wang, G.-H. Lee
135
and S.-M. Peng, Dalton Trans., 2009, 38, 3571–3573. (c)C.-S. Tsai, I.
P.-C. Liu, F.-W. Tien, G.-H. Lee, C.-Y. Yeh, C.-h. Chen and S.-M.
Peng, Inorg. Chem. Commun., 2013, 38, 152–155. (d)C.-H. Yu, M.-S.
Kuo, C.-Y. Chuang, G.-H. Lee, S.-A. Hua, B.-Y. Jin and S.-M. Peng, Chem. Asian J., 2014, 9, 3111–3115.
21. (a) C.-Y. Yeh, C.-H. Chou, K.-C. Pan, C.-C. Wang, G.-H. Lee, Y.-O.
Su and S.-M. Peng, J. Chem. Soc., Dalton Trans., 2002, 31, 2670–
2677. (b) W.-Z. Wang, R. H. Ismayilov, R.-R. Wang, Y.-L. Huang, C.-Y. Yeh, G.-H. Lee and S.-M. Peng, Dalton Trans., 2008, 37, 6808–
6816. (c)W.-Z. Wang, Y. Wu, R. H. Ismayilov, J.-H. Kuo, C.-Y. Yeh, H.-W. Lee, M.-D. Fu, C.-h. Chen, G.-H. Lee and S.-M. Peng, Dalton Trans., 2014, 43, 6229–6235.
22. T.-B. Tsao, S.-S. Lo, C.-Y. Yeh, G.-H. Lee and S.-M. Peng, Polyhedron, 2007, 26, 3833–3841.
23. 蔣青宏，2008年國立台灣大學化學系研究所博士論文
24. O. Kahn, Molecular Magnetism, Wiley-VCH, New York, 1993.
25. A. Bencini, E. Berti, A. Caneschi, D. Gatteschi, E. Giannasi and I.
Invernizzi,Chem. Eur. J., 2002, 8, No. 16, 3660–3670.
26. 林正城，1996年國立台灣大學化學系研究所博士論文
27. R. Clérac, F. A. Cotton, K. R. Dunbar, C. A. Murillo, I. Pascual and X.
Wang, Inorg. Chem., 1999, 38, 2655–2657.
28. C.-C. Yang, I. P.-C. Liu, Y.-J. Hsu, G.-H. Lee, C.-h. Chen and S.-M.
Peng, Eur. J. Inorg. Chem., 2013, 263–268.
29. J. F. Berry, F. A. Cotton and C. A. Murillo, Dalton Trans., 2003, 32, 3015–3021.
136
30. F. A. Cotton, C. A. Murillo, Q. Wang, Inorg. Chem. Commun., 2007, 10, 1088–1090.
31. R. H. Ismayilov, W.-Z. Wang, G.-H. Lee, R.-R. Wang, I. P.-C. Liu, C.-Y. Yeh and S.-M. Peng, Dalton Trans., 2007, 36, 2898–2907.
32. C.-W. Yeh, I. P.-C. Liu, R.-R. Wang, C.-Y. Yeh, G.-H. Lee and S.-M.
Peng, Eur. J. Inorg. Chem., 2010, 3153–3159.
33. C.-C. Wang, W.-C. Lo, C.-C. Chou, G.-H. Lee, J.-M. Chen and S.-M.
Peng, Inorg. Chem., 1998, 37, 4059–4065.
34. C.-X. Yin, F.-J. Huo, W.-Z. Wang, R. H. Ismayilov, G.-H. Lee, C.-Y.
Yeh, S.-M. Peng and P. Yang, Chin. J. Chem., 2009, 27, 1295–1299.
35. W.-Z. Wang, D. Zhao, T.-B. Tsao, R. Ismayilov, G.-H. Lee and S.-M.
Peng, Eur. J. Inorg. Chem., 2015, 4329–4334.
36. R. H. Ismayilov, W.-Z. Wang, G.-H. Lee, C.-H. Chien, C.-H. Jiang, C.-L. Chiu, C.-Y. Yeh and S.-M. Peng, Eur. J. Inorg. Chem., 2009, 2110–2120.
37. R. H. Ismayilov, W.-Z. Wang, R.-R. Wang, Y.-L. Huang, C.-Y. Yeh, G.-H. Lee and S.-M. Peng, Eur. J. Inorg. Chem., 2008, 4290–4295.
38. S.-A. Hua, I. P.-C. Liu, H. Hasanov, G.-C. Huang, R. H. Ismayilov, C.-L. Chiu, C.-Y. Yeh, G.-H. Lee and S.-M. Peng, Dalton Trans., 2010, 39, 3890–3896.
39. J.-H. Kuo, T.-B. Tsao, G.-H. Lee, H.-W. Lee, C.-Y. Yeh and S.-M.
Peng, Eur. J. Inorg. Chem., 2011, 2025–2028.
40. 王瑞仁，2007年國立台灣大學化學系研究所博士論文 41. 謝長霖，2005年國立台灣大學化學系研究所碩士論文 42. 黃淯凱，2007年國立台灣大學化學系研究所碩士論文
137
43. F. A. Cotton and R. Poli, Inorg. Chem., 1987, 26, 3652–3653.
44. R. L. Bodner and D. G. Hendricker, Inorg. Chem., 1973, 12, 33–37.
45. 曹廷賓，2005年國立台灣大學化學系研究所博士論文
46. C. Yin, G.-C. uang, C.-K. Kuo, M.-D. Fu, H.-C. Lu, J.-H. Ke, K.-N.
Shih, Y.-L. Huang, G.-H. Lee, C.-Y. Yeh, C.-h. Chen and S.-M. Peng, J. Am. Chem. Soc., 2008, 130, 10090–10092.
47. 華紹安，2012年國立台灣大學化學系研究所博士論文
48. (a) X. Li, J. He, J. Hihath, B. Xu, S. M. Lindsay, N. Tao, J. Am. Chem.
Soc., 2006, 128, 2135–2141. (b) B. Xu, N. J. Tao, Science, 2003, 301, 1221–1223. (c) B. Kim, J. M. Beebe, C. Olivier, S. Rigaut, D.
Touchard, J. G. Kushmerick, X. Zhu, C. D. Frisbie, J. Phys. Chem. C, 2007, 111, 7521–7526. (d) A. S. Blum, T. Ren, D. A. Parish, S. A.
Trammell, M. H. Moore, J. G. Kushmerick, G. Xu, J. R. Deschamps, S. K. Pollack, R. Shashidhar, J. Am. Chem. Soc., 2005, 127, 10010–
10011. (e) A. K. Mahapatro, J. Ying, T. Ren, D. B. Janes, Nano Lett., 2008, 8, 2131–2136. (f) R. Mas-Ballesté, J. Gómez-Herrero, F.
Zamora, Chem. Soc. Rev., 2010, 39, 4220–4233.
49. C. Mealli, D. M. Proserpio, J. Chem. Edu. 1990, 67, 399–402.
138
附錄
光譜與晶體數據
139
Appendix A. IR, NMR, Mass spectra about starting materials, ligands and the corresponding complexes
Figure A-1 IR spectrum of 2-amino-7-hydroxy-1,8-naphthyridine.
Figure A-2 1H NMR spectrum of 2-amino-7-hydroxy-1,8- naphthyridine was taken at 400 MHz in DMSO-d6 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
617.15661.98714.05783.47833.61874.1932.92976.791111.78
1228.441268.461289.671370.661400.55
1511.431547.111634.85
3166.94
3387.74
No cm-1 %T Intensity 1 537.12 77.200 W 2 617.15 46.200 S 3 661.98 74.800 W 4 714.05 81.900 W 5 783.47 72.800 W
No cm-1 %T Intensity 6 833.61 65.100 M 7 874.10 71.000 M 8 932.92 75.400 W 9 976.79 78.600 W 10 1111.78 32.000 S
No cm-1 %T Intensity 11 1228.44 72.200 W 12 1268.46 77.300 W 13 1289.67 80.500 W 14 1370.66 45.800 S 15 1400.55 40.400 S
No cm-1 %T Intensity 16 1511.43 48.900 S 17 1547.11 61.300 M 18 1634.85 22.600 VS 19 3166.94 29.400 VS 20 3387.74 45.900 S
b,c
-OH
-NH2
d a
140
Figure A-3 FAB-MS spectrum of 2-amino-7-hydroxy-1,8-naphthyridine.
Figure A-4 IR spectrum of 2,7-dihydroxy-1,8-naphthyridine.
4000 3000 2000 1000
Wavenumber (cm-1)
930.511013.911040.431114.671146.01
1228.931282.921358.611402.481487.811507.58
1638.22
1916.87
2803.93
3035.33
3405.1
No cm-1 %T Intensity 1 549.66 52.900 M 2 618.11 61.500 M 3 639.33 61.300 M 4 672.59 63.000 M 5 714.53 64.800 M 6 777.20 49.100 M
No cm-1 %T Intensity 7 836.02 39.800 S 8 865.43 66.100 M 9 930.51 65.900 M 10 1013.91 59.500 M 11 1040.43 64.200 M 12 1114.67 54.100 M
No cm-1 %T Intensity 13 1146.01 40.400 S 14 1228.93 47.400 M 15 1282.92 47.600 M 16 1358.61 33.300 S 17 1402.48 24.200 S 18 1487.81 31.700 S
No cm-1 %T Intensity 19 1507.58 31.300 S 20 1638.22 12.800 VS 21 1916.87 70.000 W 22 2803.93 42.900 S 23 3035.33 36.000 S 24 3405.10 47.700 M
[M+H]+
C8H7N3O
Exact Mass: 161.08
141
Figure A-5 1H NMR spectrum of 2,7-dihydroxy-1,8- naphthyridine was taken at 400 MHz in DMSO-d6 at 298 K.
Figure A-6 FAB-MS spectrum of 2,7-dihydroxy-1,8-naphthyridine.
b a
[M+H]+
C8H6N2O2
Exact Mass: 162.07
142
Figure A-7 IR spectrum of 2-7-dichloro-1,8-naphthyridine.
Figure A-8 1H NMR spectrum of 2-7-dichloro-1,8- naphthyridine was taken at 400 MHz in DMSO-d6 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 3093.66 3045.94 2985.68 1994.97 1964.6 1667.15 1584.71 1538.43 1473.35 1422.731367.29 1307.51 1267.98 1141.18 1124.79 997.52 943.04923.28 850.96 794.08 781.54 658.61 614.74
No cm-1 %T Intensity 1 614.74 46.000 M 2 658.61 49.700 M 3 781.54 25.000 S 4 794.08 19.500 S 5 850.96 14.800 VS 6 923.28 31.300 S
No cm-1 %T Intensity 7 943.04 52.500 M 8 997.52 64.500 M 9 1124.79 11.600 VS 10 1141.18 18.300 VS 11 1267.98 59.900 M 12 1307.51 32.300 S
No cm-1 %T Intensity 13 1367.29 61.000 M 14 1391.87 62.300 M 15 1422.73 35.300 S 16 1473.35 23.400 S 17 1538.43 17.800 VS 18 1584.71 15.900 VS
No cm-1 %T Intensity 19 1667.15 69.700 W 20 1964.60 65.600 M 21 1994.97 65.700 M 22 2985.68 44.000 M 23 3045.94 23.600 S 24 3093.66 51.700 M
b a
143
Figure A-9 FAB-MS spectrum of 2-7-dichloro-1,8-naphthyridine.
Figure A-10 IR spectrum of 2-amino-5-phenylpyridine.
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 555.44586.78646.56699.1747.31771.42831.2
993.661002.82
1075.141147.931181.21258.331321.011385.611447.81482.511515.291576.521609.31657.02
1952.55
2741.25
3029.553057.993158.75
3353.51
No cm-1 %T Intensity 1 518.80 40.100 W 2 555.44 43.700 W 3 586.78 39.100 W 4 646.56 41.000 W 5 699.10 22.000 S 6 747.31 35.100 M 7 771.42 25.700 S 8 831.20 29.100 S
No cm-1 %T Intensity 9 911.71 44.800 W 10 934.85 43.500 W 11 969.08 44.800 W 12 993.66 42.500 W 13 1002.82 39.300 W 14 1026.45 41.500 W 15 1075.14 41.200 W 16 1147.93 37.300 M
No cm-1 %T Intensity 17 1181.20 41.300 W 18 1258.33 31.300 M 19 1321.01 32.600 M 20 1385.61 24.200 S 21 1447.80 32.300 M 22 1482.51 17.900 VS 23 1515.29 23.600 S 24 1576.52 35.500 M
No cm-1 %T Intensity 25 1609.30 22.500 S 26 1657.02 23.200 S 27 1952.55 42.200 W 28 2741.25 36.500 M 29 3029.55 30.300 M 30 3057.99 30.700 M 31 3158.75 22.700 S 32 3353.51 24.300 S
[M+H]+
C8H4N2Cl2
Exact Mass: 198.96
144
Figure A-11 1H NMR spectrum of 2-amino-5-phenylpyridine was taken at 400 MHz in DMSO-d6 at 298 K.
Figure A-12 FAB-MS spectrum of 2-amino-5-phenylpyridine.
a b d e
f c -NH2
[M+H]+
C11H10N2
Exact Mass: 170.10
145
Figure A-13 IR spectrum of 2-amino-5-phenylpyrimidine.
Figure A-14 1H NMR spectrum of 2-amino-5-phenylpyrimidine was taken at 400 MHz in DMSO-d6 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 535.67569.9663.91696.69754.55798.9
907.85951.241028.371062.121204.8212271300.761331.131383.21448.281488.771520.591549.041596.76
1684.021749.1
1875.411948.21
2145.87
2731.13
3007.85
3151.52
3309.64
No cm-1 %T Intensity 1 535.67 28.300 S 2 569.90 34.300 S 3 663.91 49.000 M 4 673.07 53.800 M 5 696.69 18.900 S 6 754.55 27.700 S 7 798.90 29.400 S 8 907.85 64.200 W
No cm-1 %T Intensity 9 951.24 44.500 M 10 973.90 60.800 W 11 1004.27 61.300 W 12 1028.37 59.000 W 13 1062.12 55.300 M 14 1204.82 35.100 S 15 1227.00 30.300 S 16 1300.76 38.500 M
No cm-1 %T Intensity 17 1331.13 49.900 M 18 1383.20 27.700 S 19 1448.28 26.500 S 20 1488.77 16.500 S 21 1520.59 11.600 VS 22 1549.04 33.000 S 23 1596.76 20.500 S 24 1684.02 7.690 VS
No cm-1 %T Intensity 25 1749.10 72.100 VW 26 1875.41 62.600 W 27 1948.21 60.600 W 28 2145.87 55.000 M 29 2731.13 37.600 M 30 3007.85 29.300 S 31 3151.52 19.400 S 32 3309.64 19.000 S
b a
d c -NH2
146
Figure A-15 FAB-MS spectrum of 2-amino-5-phenylpyrimidine.
Figure A-16 IR spectrum of 2-amino-5-phenylpyrazine.
4000 3000 2000 1000
Wavenumber (cm-1)
924.241010.061025.961057.3
1197.591216.391296.421340.291387.531447.311479.131536.981588.091650.28
1931.82
2710.4
3015.56
3168.87
3333.75
No cm-1 %T Intensity 1 513.02 66.300 M 2 558.33 67.300 W 3 594.49 68.300 W 4 653.31 70.400 W 5 695.25 61.300 M 6 752.14 66.100 M 7 783.47 68.700 W 8 867.36 70.100 W
No cm-1 %T Intensity 9 883.26 65.900 M 10 905.92 69.800 W 11 924.24 69.200 W 12 959.92 69.300 W 13 1010.06 61.800 M 14 1025.96 64.300 M 15 1057.30 67.700 W 16 1060.67 68.100 W
No cm-1 %T Intensity 17 1074.17 68.000 W 18 1197.59 64.900 M 19 1216.39 62.700 M 20 1296.42 66.600 W 21 1340.29 65.900 M 22 1387.53 53.700 S 23 1447.31 61.600 M 24 1479.13 56.200 S
No cm-1 %T Intensity 25 1536.98 51.200 VS 26 1588.09 59.300 S 27 1650.28 53.500 S 28 1931.82 69.500 W 29 2710.40 65.700 M 30 3015.56 61.200 M 31 3168.87 52.100 VS 32 3333.75 55.800 S
[M+H]+
C10H9N3
Exact Mass: 171.10
147
Figure A-17 1H NMR spectrum of 2-amino-5-phenylpyrazine was taken at 400 MHz in DMSO-d6 at 298 K.
Figure A-18 FAB-MS spectrum of 2-amino-5-phenylpyrazine.
b a
c d
e
-NH2
[M+H]+
C10H9N3
Exact Mass: 171.10
148
Figure A-19 IR spectrum of
2,7-bis(5-phenylpyridylamino)-1,8-naphthyridine (H2bphpyany).
Figure A-20 1H NMR spectrum of
2,7-bis(5-phenylpyridylamino)-1,8-naphthyridine (H2bphpyany) was taken at 400 MHz in DMSO-d6 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
599.31694.77742.98766.12
835.54905.921004.271028.371075.141139.74
1226.031253.991336.911376.451448.281477.21513.361599.66
3028.13059.44
3274.93
No cm-1 %T Intensity 1 504.34 74.200 W 2 549.17 80.200 W 3 599.31 79.000 W 4 694.77 66.600 M 5 742.98 77.100 W 6 766.12 62.600 M
No cm-1 %T Intensity 7 796.97 72.600 W 8 835.54 70.100 M 9 905.92 83.900 VW 10 1004.27 78.000 W 11 1028.37 78.500 W 12 1075.14 81.700 W
No cm-1 %T Intensity 13 1139.74 62.800 M 14 1226.03 69.400 M 15 1253.99 71.400 M 16 1336.91 38.200 VS 17 1376.45 42.800 VS 18 1448.28 52.700 S
No cm-1 %T Intensity 19 1477.20 42.200 VS 20 1513.36 38.900 VS 21 1599.66 38.600 VS 22 3028.10 64.400 M 23 3059.44 65.000 M 24 3274.93 61.400 M
a b h
149
Figure A-21 MALDI-MS spectrum of
2,7-bis(5-phenylpyridylamino)-1,8-naphthyridine (H2bphpyany).
Figure A-22 IR spectrum of
2,7-bis(5-phenylpyrimidylamino)-1,8-naphthyridine (H2bphpmany).
4000 3000 2000 1000
Wavenumber (cm-1)
614.74651.38691.87755.99798.9845.18
945.941031.271062.61135.881174.93
1307.511359.571427.071498.421536.021592.42
3230.58
3403.17
No cm-1 %T Intensity 1 503.37 62.200 W 2 576.17 67.400 W 3 614.74 65.700 W 4 651.38 53.600 M 5 665.36 63.600 W 6 691.87 45.500 M
No cm-1 %T Intensity 7 755.99 50.300 M 8 798.90 40.700 M 9 845.18 53.000 M 10 945.94 65.300 W 11 1031.27 58.600 W 12 1062.60 57.900 W
No cm-1 %T Intensity 13 1135.88 36.100 M 14 1174.93 52.200 M 15 1307.51 11.700 VS 16 1359.57 21.300 S 17 1388.50 24.300 S 18 1427.07 6.950 VS
No cm-1 %T Intensity 19 1453.58 24.400 S 20 1498.42 17.500 S 21 1536.02 26.100 S 22 1592.42 15.600 S 23 3230.58 38.000 M 24 3403.17 37.700 M
[M+H]+
C30H22N6
Exact Mass: 466.24
150
Figure A-23 MALDI-MS spectrum of
2,7-bis(5-phenylpyrimidylamino)-1,8-naphthyridine (H2bphpmany).
Figure A-24 IR spectrum of
2,7-bis(5-phenylpyrazinamino)-1,8-naphthyridine (H2bphpzany).
4000 3000 2000 1000
Wavenumber (cm-1)
797.93850.96899.17
1011.981026.45
1143.61166.74
1311.851356.21388.51443.461472.381503.241529.751578.441610.26
3037.743061.853127.89
3305.793361.71
No cm-1 %T Intensity 1 547.73 94.500 W 2 565.08 93.900 W 3 617.15 93.100 W 4 690.91 85.200 M 5 744.90 86.500 M 6 784.44 93.700 W 7 797.93 90.200 W
No cm-1 %T Intensity 8 850.96 90.000 W 9 899.17 93.500 W 10 1011.98 89.500 W 11 1026.45 91.700 W 12 1143.60 80.000 M 13 1166.74 81.800 M 14 1311.85 71.800 S
No cm-1 %T Intensity 15 1356.20 75.800 M 16 1388.50 52.200 VS 17 1443.46 80.100 M 18 1472.38 69.100 S 19 1503.24 55.300 VS 20 1529.75 65.200 S 21 1578.44 80.600 M
No cm-1 %T Intensity 22 1595.32 70.700 S 23 1610.26 65.000 S 24 3037.74 89.800 W 25 3061.85 89.700 W 26 3127.89 90.000 W 27 3305.79 86.800 M 28 3361.71 87.600 M
[M+H]+
C28H20N8
Exact Mass: 468.24
151
Figure A-25 1H NMR spectrum of
2,7-bis(5-phenylpyrazinamino)-1,8-naphthyridine (H2bphpzany) was taken at 400 MHz in DMSO-d6 at 298 K.
Figure A-26 MALDI-MS spectrum of
2,7-bis(5-phenylpyrazinamino)-1,8-naphthyridine (H2bphpzany).
-NH2
d
c a, e b, f g
[M+H]+
C28H20N8
Exact Mass: 468.24
152
Figure A-27 IR spectrum of
2,7-bis(5-phenylpyridylamino)-1,8-naphthyridine (H2bnpyany).
Figure A-28 1H NMR spectrum of
2,7-bis(5-phenylpyridylamino)-1,8-naphthyridine (H2bnpyany) was taken at 400 MHz in DMSO-d6 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
1114.191138.291221.211233.751283.881326.311398.621432.851498.91578.931596.28
3072.453106.683198.763268.18
3380.51
No cm-1 %T Intensity 1 528.93 74.500 W 2 570.87 69.700 W 3 613.29 69.500 W 4 637.40 71.800 W 5 690.91 67.700 W 6 717.91 68.600 W 7 736.71 71.000 W 8 764.67 54.800 M
No cm-1 %T Intensity 9 797.93 60.800 M 10 845.66 49.700 M 11 879.89 77.400 W 12 941.60 77.400 W 13 978.24 75.500 W 14 1013.91 61.400 M 15 1114.19 32.200 S 16 1138.29 48.300 M
No cm-1 %T Intensity 17 1221.21 32.300 S 18 1233.75 33.900 S 19 1283.88 17.000 S 20 1326.31 7.880 VS 21 1398.62 41.100 M 22 1432.85 39.600 S 23 1467.56 45.200 M 24 1498.90 19.000 S
No cm-1 %T Intensity 25 1543.25 35.800 S 26 1578.93 24.100 S 27 1596.28 14.300 VS 28 3072.45 47.700 M 29 3106.68 47.800 M 30 3198.76 47.700 M 31 3268.18 45.200 M 32 3380.51 50.200 M
e
-NH2
d c a b
153
Figure A-29 MALDI-MS spectrum of
2,7-bis(5-phenylpyridylamino)-1,8-naphthyridine (H2bnpyany).
Figure A-30 IR spectrum of
2,7-bis(4-methylpyrimidylamino)-1,8-naphthyridine (H2bmpmany).
4000 3000 2000 1000
Wavenumber (cm-1)
1141.181279.551308.471328.241373.551408.261503.721577.481612.19
2135.74
3038.71
3230.58
3401.72
No cm-1 %T Intensity 1 547.25 57.100 M 2 573.28 59.600 M 3 620.04 59.900 M 4 654.27 62.200 M 5 701.52 58.300 M 6 744.42 55.800 M
No cm-1 %T Intensity 7 798.90 35.200 S 8 810.47 43.900 M 9 846.63 49.000 M 10 994.15 70.800 W 11 1037.05 71.700 W 12 1141.18 36.000 S
No cm-1 %T Intensity 13 1279.55 21.400 S 14 1308.47 16.000 VS 15 1328.24 14.100 VS 16 1373.55 17.300 VS 17 1408.26 10.300 VS 18 1503.72 11.200 VS
No cm-1 %T Intensity 19 1577.48 9.670 VS 20 1612.19 15.100 VS 21 2135.74 81.900 W 22 3038.71 42.100 S 23 3230.58 40.700 S 24 3401.72 39.600 S
[M+H]+
C18H12N8O4
Exact Mass: 404.15
154
Figure A-31 1H NMR spectrum of
2,7-bis(4-methylpyrimidylamino)-1,8-naphthyridine (H2bmpmany) was taken at 400 MHz in DMSO-d6 at 298 K.
Figure A-32 MALDI-MS spectrum of
2,7-bis(4-methylpyrimidylamino)-1,8-naphthyridine (H2bmpmany).
d, a
-NH2 b
c
e
[M+H]+ C18H16N8
Exact Mass: 344.20
155
Figure A-33 IR spectrum of [Ni6(bphpyany)4Cl2](PF6)2 (1)
Figure A-34 1H NMR spectrum of [Ni6(bphpyany)4Cl2](PF6)2 (1) was taken at 400 MHz in CD2Cl2 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 556.89583.4655.72694.28741.53769.01837.47942.56986.431010.541034.161150.831229.891293.041344.631363.431418.871467.561502.75
1593.871611.71
3028.583061.85
3643.25
No cm-1 %T Intensity 1 556.89 61.200 M 2 583.40 76.100 W 3 655.72 79.300 W 4 694.28 61.600 M 5 741.53 68.100 W 6 769.01 56.300 M
No cm-1 %T Intensity 7 837.47 37.700 S 8 942.56 82.400 VW 9 986.43 74.000 W 10 1010.54 76.400 W 11 1034.16 73.400 W 12 1150.83 39.700 S
No cm-1 %T Intensity 13 1229.89 42.700 M 14 1293.04 31.700 S 15 1344.63 26.600 S 16 1363.43 13.000 VS 17 1418.87 30.400 S 18 1467.56 10.100 VS
No cm-1 %T Intensity 19 1502.75 37.700 S 20 1593.87 32.500 S 21 1611.71 44.200 M 22 3028.58 54.100 M 23 3061.85 56.000 M 24 3643.25 51.700 M
99.67 75.11 11.18 8.74 7.99 7.76 6.98 1.29
156
Figure A-35 MALDI-MS spectrum of [Ni6(bphpyany)4Cl2](PF6)2 (1)
Figure A-36 IR spectrum of [Ni6(bphpyany)4Cl2](PF6) (2)
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 582.92654.75692.84741.53762.26828.31893.87985.951010.061033.21148.91228.931291.61343.181362.471417.911466.61500.831592.911610.74
3028.583056.06
3394.49
No cm-1 %T Intensity 1 556.89 61.600 W 2 582.92 60.100 W 3 654.75 61.600 W 4 692.84 46.500 M 5 741.53 52.000 M 6 762.26 43.200 M
No cm-1 %T Intensity 7 828.31 47.100 M 8 893.87 60.000 W 9 985.95 51.700 M 10 1010.06 53.800 W 11 1033.20 51.000 M 12 1148.90 27.000 S
No cm-1 %T Intensity 13 1228.93 28.800 S 14 1291.60 21.200 S 15 1343.18 18.200 S 16 1362.47 12.100 VS 17 1417.91 22.300 S 18 1466.60 10.800 VS
No cm-1 %T Intensity 19 1500.83 31.800 S 20 1592.91 25.300 S 21 1610.74 33.600 S 22 3028.58 33.500 S 23 3056.06 34.700 M 24 3394.49 31.000 S
[M]+ C120H80N24Cl2Ni6
Exact Mass: 2280.06
[M-NiCl2]+
157
Figure A-37 IR spectrum of [Ni6(bphpyany)4(NCS)2](PF6)2 (3)
Figure A-38 1H NMR spectrum of [Ni6(bphpyany)4(NCS)2](PF6)2 (3) was taken at 400 MHz in CD2Cl2 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 556.4583.88655.72691.39741.05760.81828.31
985.951034.641053.931075.621149.861229.411291.61343.181362.471418.391466.61502.75
1593.871612.19
2052.82
3028.583056.06
3654.82
No cm-1 %T Intensity 1 556.40 57.800 M 2 583.88 72.400 W 3 655.72 72.000 W 4 691.39 54.900 M 5 741.05 59.300 M 6 760.81 50.300 M 7 828.31 36.000 S
No cm-1 %T Intensity 8 934.85 75.100 W 9 985.95 64.900 W 10 1010.54 67.800 W 11 1034.64 63.500 W 12 1053.93 66.700 W 13 1075.62 67.200 W 14 1149.86 35.400 S
No cm-1 %T Intensity 15 1229.41 37.000 S 16 1291.60 29.300 S 17 1343.18 23.200 S 18 1362.47 14.300 VS 19 1418.39 27.800 S 20 1447.80 32.400 S 21 1466.60 13.100 VS
No cm-1 %T Intensity 22 1502.75 34.600 S 23 1593.87 31.300 S 24 1612.19 42.400 M 25 2052.82 40.500 S 26 3028.58 47.700 M 27 3056.06 49.000 M 28 3654.82 44.900 M
101.07 77.54 11.16 8.86 8.06 7.85 7.01 1.29
158
Figure A-39 MALDI-MS spectrum of [Ni6(bphpyany)4(NCS)2](PF6)2 (3)
Figure A-40 IR spectrum of [Ni6(bphpmany)4Cl2](PF6)2 (4)
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 557.37666.32696.21757.44783.95840.36951.24989.331035.121068.871160.951232.781260.741298.831363.431426.11513.361537.471593.391610.26
3029.553056.06
3418.59
3637.47
No cm-1 %T Intensity 1 557.37 58.900 M 2 581.96 74.400 W 3 666.32 71.900 W 4 696.21 62.200 M 5 757.44 61.000 M 6 783.95 53.100 M 7 840.36 35.600 S
No cm-1 %T Intensity 8 917.98 80.700 W 9 951.24 78.700 W 10 989.33 74.200 W 11 1010.06 80.000 W 12 1035.12 71.400 W 13 1068.87 70.000 W 14 1160.95 39.700 S
No cm-1 %T Intensity 15 1184.09 65.000 M 16 1232.78 52.900 M 17 1260.74 55.600 M 18 1298.83 32.100 S 19 1363.43 12.600 VS 20 1426.10 8.810 VS 21 1513.36 46.500 M
No cm-1 %T Intensity 22 1537.47 56.000 M 23 1593.39 41.900 M 24 1610.26 50.300 M 25 3029.55 57.300 M 26 3056.06 56.900 M 27 3418.59 51.200 M 28 3637.47 53.100 M
[M]+
C112H80N26S2Ni6
Exact Mass: 2325.31
[M-Ni(NCS)2]+
159
Figure A-41 1H NMR spectrum of [Ni6(bphpmany)4Cl2](PF6)2 (4) was taken at 400 MHz in CD2Cl2 at 298 K.
Figure A-42 MALDI-MS spectrum of [Ni6(bphpmany)4Cl2](PF6)2 (4)
109.33 18.37
9.22 8.14 7.51 7.00 1.32
[M]+
C112H72N32Cl2Ni6
Exact Mass: 2288.06
[M-NiCl2]+
160
Figure A-43 IR spectrum of [Ni6(bphpmany)4Cl2](PF6) (5)
Figure A-44 1H NMR spectrum of [Ni6(bphpmany)4Cl2](PF6) (5) (●) mixing with [Ni6(bphpmany)4Cl2](PF6)2 (4) (●) was taken at 400 MHz in CD2Cl2 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
666.29695.21756.44787.3841.29950.25989.791033.661067.891150.811180.71255.431298.341362.941415.981497.941535.541593.88
3007.933054.69
3397.96
No cm-1 %T Intensity 1 557.33 76.377 W 2 581.43 76.767 W 3 666.29 76.575 W 4 695.21 67.713 M 5 756.44 69.171 M 6 787.30 64.742 M
No cm-1 %T Intensity 7 841.29 64.502 M 8 914.58 84.701 W 9 950.25 83.511 W 10 989.79 83.389 W 11 1033.66 74.924 W 12 1067.89 76.000 W
No cm-1 %T Intensity 13 1150.81 52.329 M 14 1180.70 70.910 M 15 1255.43 55.073 M 16 1298.34 33.306 S 17 1362.94 23.832 S 18 1415.98 10.369 VS
No cm-1 %T Intensity 19 1497.94 60.814 M 20 1535.54 68.247 M 21 1593.88 43.935 S 22 3007.93 65.923 M 23 3054.69 64.415 M 24 3397.96 58.446 M
75.53 22.17 18.35 15.02 13.15
9.31 1.297.007.508.11
161
Figure A-45 IR spectrum of [Co6(bphpyany)4(NCS)2](PF6) (6)
Figure A-46 1H NMR spectrum of [Co6(bphpyany)4(NCS)2](PF6) (6) was taken at 400 MHz in CD2Cl2 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
1295.451309.441338.361360.061418.871465.631499.38
1609.78
2054.27
3027.623052.69
3649.04
No cm-1 %T Intensity 1 557.37 90.200 W 2 587.74 93.400 VW 3 695.25 83.600 W 4 738.64 89.000 W 5 760.33 79.100 W 6 821.07 80.200 W
No cm-1 %T Intensity 7 844.70 79.300 W 8 1036.57 87.200 W 9 1146.49 63.100 M 10 1225.55 75.600 M 11 1295.45 71.000 M 12 1309.44 70.000 M
No cm-1 %T Intensity 13 1338.36 45.500 S 14 1360.06 28.900 VS 15 1398.14 68.000 M 16 1418.87 48.900 S 17 1465.63 27.400 VS 18 1499.38 68.200 M
No cm-1 %T Intensity 19 1589.05 74.900 M 20 1609.78 71.000 M 21 2054.27 57.900 M 22 3027.62 74.200 M 23 3052.69 74.900 M 24 3649.04 70.600 M
9.77 9.14 7.60
7.39
6.94 5.68 1.27
7.77
162
Figure A-47 1H NMR spectrum of [Co6(bphpyany)4(NCS)2](PF6) (6) was taken at 400 MHz in DMSO-d6 at 298 K.
Figure A-48 HH-COSY spectrum of [Co6(bphpyany)4(NCS)2](PF6) (6) was taken at 400 MHz in DMSO-d6 at 298 K.
9.92 9.39 7.59 7.32 6.94 4.92
6.46 1.72
163
Figure A-49 MALDI-MS spectrum of [Co6(bphpyany)4(NCS)2](PF6) (6)
Figure A-50 IR spectrum of [Co6(bphpyany)4(NCS)2](PF6)2 (7)
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 556.4585.81634.99692.36757.92822.52838.91
982.581036.09
1147.45
1230.851294.971343.181362.951420.81465.631500.83
1609.78
2049.45
3028.583056.06
3650.48
No cm-1 %T Intensity 1 556.40 32.200 M 2 585.81 39.800 W 3 634.99 40.100 VW 4 692.36 30.600 M 5 738.64 32.900 M 6 757.92 28.000 M
No cm-1 %T Intensity 7 822.52 22.100 S 8 838.91 21.100 S 9 982.58 37.300 W 10 1036.09 34.500 W 11 1147.45 22.300 S 12 1230.85 24.600 M
No cm-1 %T Intensity 13 1294.97 23.500 M 14 1343.18 15.500 S 15 1362.95 13.100 S 16 1399.59 23.100 M 17 1420.80 18.900 S 18 1465.63 9.260 VS
No cm-1 %T Intensity 19 1500.83 27.800 M 20 1609.78 23.300 M 21 2049.45 19.600 S 22 3028.58 24.600 M 23 3056.06 24.800 M 24 3650.48 23.700 M
[M]+ C122H80N26S2Co6
Exact Mass: 2326.65
[M-Co(NCS)2]+ [M-NCS]+
164
Figure A-51 1H NMR spectrum of [Co6(bphpyany)4(NCS)2](PF6)2 (7) was taken at 400 MHz in DMSO-d6 at 298 K.
Figure A-52 IR spectrum of [Co5(bphpzany)4(NCS)2] (8)
4000 3000 2000 1000
Wavenumber (cm-1)
1145.041180.721256.891277.621334.991356.21373.071428.991445.391472.861501.31
1603.03
2048
3026.17
No cm-1 %T Intensity 1 585.81 88.400 W 2 655.23 81.400 W 3 689.46 81.500 W 4 743.94 81.300 W 5 781.54 81.200 W 6 796.49 86.200 W
No cm-1 %T Intensity 7 835.54 86.600 W 8 902.07 84.500 W 9 961.36 81.000 W 10 1037.05 71.600 M 11 1145.04 57.300 S 12 1180.72 62.200 M
No cm-1 %T Intensity 13 1256.89 72.000 M 14 1277.62 72.300 M 15 1334.99 53.600 S 16 1356.20 44.200 S 17 1373.07 45.000 S 18 1428.99 56.700 S
No cm-1 %T Intensity 19 1445.39 45.500 S 20 1472.86 34.200 VS 21 1501.31 46.200 S 22 1603.03 61.200 M 23 2048.00 60.800 M 24 3026.17 71.700 M
35.81 12.61 8.86 8.27 7.29 6.29 1.89 -3.09
165
Figure A-53 1H NMR spectrum of [Co5(bphpzany)4(NCS)2] (8) was taken at 400 MHz in CD2Cl2 at 298 K.
Figure A-54 1H NMR spectrum of [Co5(bphpzany)4(NCS)2] (8) was taken at 400 MHz in DMSO-d6 at 298 K.
63.45 15.74
8.74 8.14 7.387.49 15.97
8.51 7.97 7.467.67
64.25
166
Figure A-55 MALDI-MS spectrum of [Co5(bphpzany)4(NCS)2] (8)
Figure A-56 IR spectrum of [Co5(bphpzany)4(OTf)2] (9)
4000 3000 2000 1000
Wavenumber (cm-1)
1144.561179.751258.331280.51 1335.951355.231375.961430.441446.351472.861501.79
1603.51
3059.44
3446.07
No cm-1 %T Intensity 1 515.43 79.500 W 2 582.44 78.100 W 3 634.99 60.500 M 4 655.72 68.500 M 5 691.39 68.100 M 6 744.90 66.800 M 7 782.02 67.400 M
No cm-1 %T Intensity 8 835.06 77.200 W 9 900.62 74.700 W 10 962.33 69.600 M 11 1023.07 49.900 M 12 1144.56 35.400 S 13 1179.75 41.700 S 14 1211.57 49.800 M
No cm-1 %T Intensity 15 1234.23 45.500 S 16 1258.33 53.900 M 17 1280.51 54.500 M 18 1305.10 46.000 S 19 1335.95 39.800 S 20 1355.23 31.100 S 21 1375.96 29.000 S
No cm-1 %T Intensity 22 1430.44 42.200 S 23 1446.35 27.900 S 24 1472.86 16.800 VS 25 1501.79 29.900 S 26 1603.51 47.000 S 27 3059.44 63.200 M 28 3446.07 62.500 M
[M+H]+ C114H72N34S2Co5
Exact Mass: 2275.70
[M-2NCS]+
167
Figure A-57 1H NMR spectrum of [Co5(bphpzany)4(OTf)2] (9) was taken at 400 MHz in CD2Cl2 at 298 K.
Figure A-58 MALDI-MS spectrum of [Co5(bphpyany)4(OTf)2] (9)
63.89 15.848.96 8.428.12 7.357.48 1.66 1.28 0.89
C114H72N32S2O6F6Co5
Exact Mass: 2475.68 [M-2OTf]+
168
Figure A-59 IR spectrum of [Co6(bphpzany)4(NCS)2](PF6) (10)
Figure A-60 1H NMR spectrum of [Co6(bphpzany)4(NCS)2](PF6) (10) was taken at 400 MHz in CD2Cl2 at 298 K.
4000 3000 2000 1000
Wavenumber (cm-1)
%Transmittance 3634.2 3454.37 3058.55 2044.66 1607.86 1500.83 1465.63 1444.91400.55 1364.87 1342.71299.3 1235.18 1176.85 1151.78 1037.52 982.07 905.42 835.99 778.62 745.83 691.36 557.81
No cm-1 %T Intensity 1 557.81 82.497 W 2 691.36 69.550 W 3 745.83 68.069 W 4 778.62 71.341 W 5 835.99 61.804 M 6 905.42 82.044 W
No cm-1 %T Intensity 7 982.07 83.317 W 8 1037.52 67.509 M 9 1151.78 37.049 S 10 1176.85 50.907 M 11 1235.18 73.108 W 12 1299.30 62.003 M
No cm-1 %T Intensity 13 1342.70 27.049 S 14 1364.87 21.367 S 15 1400.55 47.384 M 16 1417.91 37.511 S 17 1444.90 26.047 S 18 1465.63 13.482 VS
No cm-1 %T Intensity 19 1500.83 42.954 S 20 1607.86 60.955 M 21 2044.66 33.346 S 22 3058.55 54.945 M 23 3454.37 47.405 M 24 3634.20 48.175 M
9.79 9.10 7.63 7.42 6.97 5.74 1.51
169
Figure A-61 HH-COSY spectrum of [Co6(bphpzany)4(NCS)2](PF6) (10) was taken at 400 MHz in CD2Cl2 at 298 K.
Figure A-62 1H NMR spectrum of [Co6(bphpzany)4(NCS)2](PF6) (10) was taken at 400 MHz in DMSO-d6 at 298 K.
9.45 7.69 7.52 6.86 6.53 5.42 2.13
170
Figure A-63 MALDI-MS spectrum of [Co6(bphpzany)4(NCS)2](PF6) (10)
Figure A-64 MALDI-MS spectrum of [Ni5(bphpyany)4(NCS)2] (11)
[M]+ C114H72N34S2Co5
Exact Mass: 2334.65
[M-NCS]+ [M-Co(NCS)2]+
C122H80N26S2Ni5
Exact Mass: 2266.60
[M-NCS]+
[M-2NCS]+
171
Figure A-65 MALDI-MS spectrum of [Ni6(bphpmany)4(OAc)2](PF6)2
(12)
Figure A-66 MALDI-MS spectrum of [Ni6(bphpmany)4(NCS)2](PF6)2
(13)
C116H78N32O4Ni6
Exact Mass: 2335.24
[M]+
C114H72N34S2Ni6
Exact Mass: 2333.31
[M]+ [M-Ni(NCS)2]+
172
Figure A-67 MALDI-MS spectrum of [Ni6(bmpmany)4Cl2](PF6)2 (14)
Figure A-68 MALDI-MS spectrum of [Ni6(bphpzany)4Cl2](PF6)2 (15)
C72H56N32Cl2Ni6
Exact Mass: 1791.90
[M]+
[M-NiCl2]+
C112H72N32Cl2Ni6
Exact Mass: 2288.06
[M]+ [M-NiCl2]+
173
Figure A-69 MALDI-MS spectrum of [Ni6(bphpzany)4(NCS)2](PF6)2 (16)
Figure A-70 MALDI-MS spectrum of [Ni6(bpzany)4Cl2](PF6)2 (17)
C114H72N34S2Ni6
Exact Mass: 2333.31
[M]+ [M-Ni(NCS)2]+
[M-NCS]+
C64H40N32Cl2Ni6
Exact Mass: 1679.74
[M]+
174
Figure A-71 MALDI-MS spectrum of [Co5(bphpyany)4(NCS)2] (18)
Figure A-72 MALDI-MS spectrum of [Co6(bphpmany)4(NCS)2](PF6) (19)
C122H80N26S2Co5
Exact Mass: 2267.72
[M-NCS]+ [M-2NCS]+
C114H72N34S2Co6
Exact Mass: 2334.65
[M]+
175
Figure A-73 MALDI-MS spectrum of [Co5(bpmany)4(NCS)2] (20)
Figure A-74 MALDI-MS spectrum of [Co6(bpmany)4(NCS)2](PF6) (21)
C66H40N34S2Co5
Exact Mass: 1667.40
[M-2NCS]+
C66H40N34S2Co5
Exact Mass: 1726.33
[M-Co(NCS)2]+ [M]+
176
Figure A-75 MALDI-MS spectrum of [Co6(bmpmany)4Cl2](PF6) (22)
Figure A-76 MALDI-MS spectrum of [Co6(bmpmany)4(NCS)2](PF6) (23)
C72H56N32Cl2Co6
Exact Mass: 1793.24
[M-CoCl2]+ [M]+
C74H56N34S2Co6
Exact Mass: 1838.49
[M-Co(NCS)2]+ [M]+
177
Appendix B. Crystal data
B-1 [Ni6(bphpyany)4Cl2](PF6)2 (1)
Table 1. Crystal data and structure refinement for ic15412.
Identification code ic15412
Empirical formula C120H80Cl2F12N24Ni6P2
Formula weight 2569.99
Temperature 150(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group C2/c
Unit cell dimensions a = 43.5000(12) Å = 90°
b = 26.0589(8) Å = 108.3643(12)°
c = 25.4961(7) Å = 90°
Volume 27429.5(14) Å3
Z 4
Density (calculated) 1.407 Mg/m3
Absorption coefficient 1.135 mm-1
F(000) 11424
Crystal size
Theta range for data collection 1.14 to 27.46°
Index ranges -55<=h<=54, -32<=k<=33, -30<=l<=33
Reflections collected 87419
Independent reflections 29381 [R(int) = 0.0531]
Completeness to theta = 27.46° 93.6 %
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 29381 / 0 / 1521
Goodness-of-fit on F2 2.031
Final R indices [I>2sigma(I)] R1 = 0.1657, wR2 = 0.4803 R indices (all data) R1 = 0.2262, wR2 = 0.5164 Largest diff. peak and hole 7.274 and -2.174 e.Å-3
178 Table 2. Bond lengths [Å ] and angles [°] for ic15412.
___________________________________________________________________________________
Ni(1)-N(10) 2.101(10)
179
180
181
N(10)-Ni(1)-N(4) 164.4(4) N(10)-Ni(1)-N(7) 89.8(4)
N(4)-Ni(1)-N(7) 91.8(4)
N(10)-Ni(1)-N(1) 86.8(4)
N(4)-Ni(1)-N(1) 87.7(4)
N(7)-Ni(1)-N(1) 165.2(4) N(10)-Ni(1)-Cl(1) 98.6(3) N(4)-Ni(1)-Cl(1) 96.5(3) N(7)-Ni(1)-Cl(1) 97.9(3) N(1)-Ni(1)-Cl(1) 96.9(3) N(10)-Ni(1)-Ni(2) 81.4(3) N(4)-Ni(1)-Ni(2) 83.6(3) N(7)-Ni(1)-Ni(2) 81.1(2) N(1)-Ni(1)-Ni(2) 84.1(3) Cl(1)-Ni(1)-Ni(2) 179.03(12) N(8)-Ni(2)-N(11) 90.0(4) N(8)-Ni(2)-N(2) 174.7(4) N(11)-Ni(2)-N(2) 90.2(4)
N(8)-Ni(2)-N(5) 89.8(4)
N(11)-Ni(2)-N(5) 175.2(4)
N(2)-Ni(2)-N(5) 89.6(4)
N(8)-Ni(2)-Ni(3) 87.1(3) N(11)-Ni(2)-Ni(3) 88.8(3) N(2)-Ni(2)-Ni(3) 87.6(3) N(5)-Ni(2)-Ni(3) 86.4(3) N(8)-Ni(2)-Ni(1) 94.3(3) N(11)-Ni(2)-Ni(1) 93.9(3) N(2)-Ni(2)-Ni(1) 91.0(3) N(5)-Ni(2)-Ni(1) 90.9(3) Ni(3)-Ni(2)-Ni(1) 176.95(8)
N(6)-Ni(3)-N(3) 90.9(4)
N(6)-Ni(3)-N(12) 177.8(4) N(3)-Ni(3)-N(12) 91.3(4)
N(6)-Ni(3)-N(9) 88.7(4)
N(3)-Ni(3)-N(9) 179.0(4) N(12)-Ni(3)-N(9) 89.1(4) N(6)-Ni(3)-Ni(3)#1 88.5(3) N(3)-Ni(3)-Ni(3)#1 89.6(3) N(12)-Ni(3)-Ni(3)#1 91.2(3) N(9)-Ni(3)-Ni(3)#1 89.4(3) N(6)-Ni(3)-Ni(2) 91.2(3) N(3)-Ni(3)-Ni(2) 90.0(3) N(12)-Ni(3)-Ni(2) 89.1(3) N(9)-Ni(3)-Ni(2) 90.9(3) Ni(3)#1-Ni(3)-Ni(2) 179.58(8) N(13)-Ni(4)-N(19) 164.4(4) N(13)-Ni(4)-N(16) 90.5(4) N(19)-Ni(4)-N(16) 85.4(3) N(13)-Ni(4)-N(22) 92.8(4) N(19)-Ni(4)-N(22) 87.1(4) N(16)-Ni(4)-N(22) 163.4(4) N(13)-Ni(4)-Cl(2) 97.2(3) N(19)-Ni(4)-Cl(2) 98.2(3) N(16)-Ni(4)-Cl(2) 98.7(3) N(22)-Ni(4)-Cl(2) 97.0(3) N(13)-Ni(4)-Ni(5) 82.6(3) N(19)-Ni(4)-Ni(5) 82.0(3) N(16)-Ni(4)-Ni(5) 83.1(3) N(22)-Ni(4)-Ni(5) 81.2(2) Cl(2)-Ni(4)-Ni(5) 178.18(10) N(14)-Ni(5)-N(17) 89.8(4) N(14)-Ni(5)-N(20) 176.0(4) N(17)-Ni(5)-N(20) 89.2(4) N(14)-Ni(5)-N(23) 90.1(5) N(17)-Ni(5)-N(23) 174.6(4) N(20)-Ni(5)-N(23) 90.5(4) N(14)-Ni(5)-Ni(6) 88.8(3) N(17)-Ni(5)-Ni(6) 88.8(3)
182 N(20)-Ni(5)-Ni(6) 87.3(3)
N(23)-Ni(5)-Ni(6) 85.8(3) N(14)-Ni(5)-Ni(4) 92.6(3) N(17)-Ni(5)-Ni(4) 91.8(3) N(20)-Ni(5)-Ni(4) 91.3(3) N(23)-Ni(5)-Ni(4) 93.6(3) Ni(6)-Ni(5)-Ni(4) 178.50(8) N(15)-Ni(6)-N(18) 90.2(4) N(15)-Ni(6)-N(24) 90.4(4) N(18)-Ni(6)-N(24) 177.8(4) N(15)-Ni(6)-N(21) 178.8(4) N(18)-Ni(6)-N(21) 89.3(4) N(24)-Ni(6)-N(21) 90.1(4) N(15)-Ni(6)-Ni(6)#2 90.3(3) N(18)-Ni(6)-Ni(6)#2 89.8(3) N(24)-Ni(6)-Ni(6)#2 88.1(3) N(21)-Ni(6)-Ni(6)#2 88.6(3) N(15)-Ni(6)-Ni(5) 89.7(3) N(18)-Ni(6)-Ni(5) 90.1(3) N(24)-Ni(6)-Ni(5) 92.1(3) N(21)-Ni(6)-Ni(5) 91.3(3) Ni(6)#2-Ni(6)-Ni(5) 179.81(9) C(1)-N(1)-C(5) 116.3(11) C(1)-N(1)-Ni(1) 122.4(9) C(5)-N(1)-Ni(1) 121.1(8) C(12)-N(2)-C(5) 120.8(10) C(12)-N(2)-Ni(2) 119.3(7) C(5)-N(2)-Ni(2) 119.8(8) C(12)-N(3)-C(16) 121.9(10) C(12)-N(3)-Ni(3) 118.7(7) C(16)-N(3)-Ni(3) 119.3(8) C(17)-N(4)-C(21) 119.8(10) C(17)-N(4)-Ni(1) 119.9(8) C(21)-N(4)-Ni(1) 119.3(7) C(21)-N(5)-C(28) 123.6(9) C(21)-N(5)-Ni(2) 116.9(7) C(28)-N(5)-Ni(2) 119.0(7) C(28)-N(6)-C(32) 120.1(9)
C(28)-N(6)-Ni(3) 118.6(7) C(32)-N(6)-Ni(3) 121.3(7) C(37)-N(7)-C(33) 116.1(10) C(37)-N(7)-Ni(1) 123.7(7) C(33)-N(7)-Ni(1) 119.3(8) C(37)-N(8)-C(44) 121.1(9) C(37)-N(8)-Ni(2) 118.8(7) C(44)-N(8)-Ni(2) 119.9(7) C(44)-N(9)-C(48) 121.2(11) C(44)-N(9)-Ni(3) 118.3(8) C(48)-N(9)-Ni(3) 120.0(8) C(53)-N(10)-C(49) 120.2(10) C(53)-N(10)-Ni(1) 124.3(8) C(49)-N(10)-Ni(1) 115.5(8) C(60)-N(11)-C(53) 122.9(9) C(60)-N(11)-Ni(2) 119.1(7) C(53)-N(11)-Ni(2) 118.0(7) C(60)-N(12)-C(32)#1 121.3(9) C(60)-N(12)-Ni(3) 120.1(7) C(32)#1-N(12)-Ni(3) 118.2(7) C(63)-N(13)-C(67) 114.1(11) C(63)-N(13)-Ni(4) 121.8(9) C(67)-N(13)-Ni(4) 123.3(8) C(74)-N(14)-C(67) 122.9(10) C(74)-N(14)-Ni(5) 119.0(8) C(67)-N(14)-Ni(5) 117.9(8) C(122)#2-N(15)-C(74) 119.5(10) C(122)#2-N(15)-Ni(6) 120.0(9) C(74)-N(15)-Ni(6) 120.3(8) C(81)-N(16)-C(77) 118.5(10) C(81)-N(16)-Ni(4) 122.7(8) C(77)-N(16)-Ni(4) 118.8(7) C(88)-N(17)-C(81) 122.3(10) C(88)-N(17)-Ni(5) 116.5(8) C(81)-N(17)-Ni(5) 121.0(8) C(106)#2-N(18)-C(88) 120.9(9) C(106)#2-N(18)-Ni(6) 119.7(7) C(88)-N(18)-Ni(6) 118.4(7)
183 C(95)-N(19)-C(91) 116.5(10)
C(95)-N(19)-Ni(4) 123.1(8) C(91)-N(19)-Ni(4) 119.7(7) C(95)-N(20)-C(102) 124.4(10) C(95)-N(20)-Ni(5) 117.2(8) C(102)-N(20)-Ni(5) 118.1(7) C(106)-N(21)-C(102) 121.9(10) C(106)-N(21)-Ni(6) 121.5(7) C(102)-N(21)-Ni(6) 116.6(8) C(107)-N(22)-C(111) 118.7(9) C(107)-N(22)-Ni(4) 117.6(8) C(111)-N(22)-Ni(4) 122.6(7) C(118)-N(23)-C(111) 122.9(11) C(118)-N(23)-Ni(5) 121.2(8) C(111)-N(23)-Ni(5) 115.3(9) C(122)-N(24)-C(118) 121.9(10) C(122)-N(24)-Ni(6) 121.4(8) C(118)-N(24)-Ni(6) 116.4(8) C(2)-C(1)-N(1) 124.9(15) C(1)-C(2)-C(3) 117.3(14) C(1)-C(2)-C(6) 123.8(18) C(3)-C(2)-C(6) 118.9(16) C(4)-C(3)-C(2) 117.3(14) C(3)-C(4)-C(5) 122.2(15) N(1)-C(5)-C(4) 121.7(11) N(1)-C(5)-N(2) 114.8(10) C(4)-C(5)-N(2) 123.3(11)
C(11)-C(6)-C(2) 119(2)
C(11)-C(6)-C(7) 126(2)
C(2)-C(6)-C(7) 111.4(18)
C(8)-C(7)-C(6) 117(3)
C(9)-C(10)-C(11) 103(5) C(6)-C(11)-C(10) 126(4) N(2)-C(12)-N(3) 118.0(10) N(2)-C(12)-C(13) 122.6(10) N(3)-C(12)-C(13) 119.2(10) C(14)-C(13)-C(12) 120.1(11) C(15)-C(14)-C(13) 120.5(11)
C(14)-C(15)-C(14)#1 125.4(16) C(14)-C(15)-C(16) 117.3(8) C(14)#1-C(15)-C(16) 117.3(8) N(3)-C(16)-N(3)#1 118.8(14) N(3)-C(16)-C(15) 120.6(7) N(3)#1-C(16)-C(15) 120.6(7) N(4)-C(17)-C(18) 127.0(12) C(17)-C(18)-C(19) 112.7(11) C(17)-C(18)-C(22) 122.4(14) C(19)-C(18)-C(22) 124.9(13) C(20)-C(19)-C(18) 122.3(12) C(19)-C(20)-C(21) 119.2(12) N(4)-C(21)-N(5) 118.8(10) N(4)-C(21)-C(20) 118.8(10) N(5)-C(21)-C(20) 122.4(10) C(23)-C(22)-C(18) 119(2) C(23)-C(22)-C(27) 123(2) C(18)-C(22)-C(27) 115.7(18) C(22)-C(23)-C(24) 120(3) C(23)-C(24)-C(25) 112(2) C(26)-C(25)-C(24) 123(3) C(25)-C(26)-C(27) 126(3) C(22)-C(27)-C(26) 109(3) N(6)-C(28)-N(5) 117.5(9) N(6)-C(28)-C(29) 122.3(10) N(5)-C(28)-C(29) 120.1(10) C(30)-C(29)-C(28) 117.8(11) C(29)-C(30)-C(31) 121.8(10) C(62)#1-C(31)-C(32) 117.2(10) C(62)#1-C(31)-C(30) 126.7(10) C(32)-C(31)-C(30) 116.0(10) N(12)#1-C(32)-N(6) 117.3(9) N(12)#1-C(32)-C(31) 120.9(10) N(6)-C(32)-C(31) 121.8(10) C(34)-C(33)-N(7) 124.9(11) C(33)-C(34)-C(35) 116.5(11) C(33)-C(34)-C(38) 123.3(13) C(35)-C(34)-C(38) 120.1(13)
184 C(36)-C(35)-C(34) 121.7(13)
C(35)-C(36)-C(37) 119.3(12) N(8)-C(37)-N(7) 113.8(9) N(8)-C(37)-C(36) 124.7(10) N(7)-C(37)-C(36) 121.3(10) C(43)-C(38)-C(39) 122.9(14) C(43)-C(38)-C(34) 121.2(16) C(39)-C(38)-C(34) 115.7(15) C(40)-C(39)-C(38) 117.9(18) C(41)-C(40)-C(39) 119.9(19) C(40)-C(41)-C(42) 121.5(17) C(43)-C(42)-C(41) 113(2) C(38)-C(43)-C(42) 125(2) N(9)-C(44)-N(8) 116.1(10) N(9)-C(44)-C(45) 120.5(10) N(8)-C(44)-C(45) 123.4(10) C(46)-C(45)-C(44) 116.9(10) C(47)-C(46)-C(45) 123.9(12) C(46)-C(47)-C(46)#1 127.8(15) C(46)-C(47)-C(48) 116.1(8) C(46)#1-C(47)-C(48) 116.1(8) N(9)-C(48)-N(9)#1 117.4(14) N(9)-C(48)-C(47) 121.3(7) N(9)#1-C(48)-C(47) 121.3(7) N(10)-C(49)-C(50) 121.9(11) C(49)-C(50)-C(51) 116.2(11) C(49)-C(50)-C(54) 121.8(11) C(51)-C(50)-C(54) 121.9(12) C(52)-C(51)-C(50) 119.5(13) C(51)-C(52)-C(53) 121.0(12) N(10)-C(53)-N(11) 115.7(10) N(10)-C(53)-C(52) 120.1(11) N(11)-C(53)-C(52) 123.9(10) C(59)-C(54)-C(50) 124.9(15) C(59)-C(54)-C(55) 118.0(15) C(50)-C(54)-C(55) 116.9(13) C(56)-C(55)-C(54) 113(2) C(55)-C(56)-C(57) 124.1(19)
C(58)-C(57)-C(56) 119.2(16) C(57)-C(58)-C(59) 117.9(19) C(54)-C(59)-C(58) 126.9(19) N(12)-C(60)-N(11) 116.8(9) N(12)-C(60)-C(61) 118.3(9) N(11)-C(60)-C(61) 124.8(10) C(62)-C(61)-C(60) 119.4(10) C(61)-C(62)-C(31)#1 122.8(10) C(64)-C(63)-N(13) 127.1(13) C(63)-C(64)-C(65) 118.0(13) C(63)-C(64)-C(68) 118.4(14) C(65)-C(64)-C(68) 123.6(13) C(66)-C(65)-C(64) 117.6(13) C(65)-C(66)-C(67) 122.4(13) N(14)-C(67)-C(66) 125.4(11) N(14)-C(67)-N(13) 113.8(11) C(66)-C(67)-N(13) 120.9(11) C(69)-C(68)-C(64) 129.4(18) C(69)-C(68)-C(73) 109.4(18) C(64)-C(68)-C(73) 117.9(15) C(68)-C(69)-C(70) 126(3) C(69)-C(70)-C(71) 120(3) C(72)-C(71)-C(70) 115(2) C(73)-C(72)-C(71) 122(2) C(72)-C(73)-C(68) 120(2) N(14)-C(74)-N(15) 114.8(11) N(14)-C(74)-C(75) 128.3(12) N(15)-C(74)-C(75) 116.9(12) C(76)-C(75)-C(74) 122.0(14) C(75)-C(76)-C(121)#2 124.4(13) C(78)-C(77)-N(16) 122.4(12) C(77)-C(78)-C(79) 117.4(12) C(77)-C(78)-C(82) 119.7(13) C(79)-C(78)-C(82) 122.9(12) C(80)-C(79)-C(78) 118.9(12) C(79)-C(80)-C(81) 122.2(11) N(16)-C(81)-N(17) 114.3(10) N(16)-C(81)-C(80) 120.3(10)
185 N(17)-C(81)-C(80) 125.2(11)
C(83)-C(82)-C(87) 117.7(16) C(83)-C(82)-C(78) 122.2(13) C(87)-C(82)-C(78) 120.2(15) C(82)-C(83)-C(84) 120.2(13) C(85)-C(84)-C(83) 121.4(16) C(84)-C(85)-C(86) 122(3) C(85)-C(86)-C(87) 123(4) C(82)-C(87)-C(86) 115(3) N(17)-C(88)-N(18) 117.0(9) N(17)-C(88)-C(89) 124.5(10) N(18)-C(88)-C(89) 118.5(9) C(90)-C(89)-C(88) 118.5(10) C(89)-C(90)-C(105)#2 123.9(11) N(19)-C(91)-C(92) 127.6(10) C(91)-C(92)-C(93) 113.6(10) C(91)-C(92)-C(96) 121.6(10) C(93)-C(92)-C(96) 124.7(11) C(92)-C(93)-C(94) 122.3(11) C(93)-C(94)-C(95) 118.2(11) N(19)-C(95)-N(20) 115.6(11) N(19)-C(95)-C(94) 121.4(11) N(20)-C(95)-C(94) 122.5(11) C(101)-C(96)-C(97) 119.1(11) C(101)-C(96)-C(92) 121.5(11) C(97)-C(96)-C(92) 119.3(11) C(98)-C(97)-C(96) 120.3(13) C(97)-C(98)-C(99) 116.5(14) C(100)-C(99)-C(98) 122.4(12) C(99)-C(100)-C(101) 121.9(13) C(100)-C(101)-C(96) 119.7(13) N(21)-C(102)-N(20) 119.4(10) N(21)-C(102)-C(103) 118.6(10) N(20)-C(102)-C(103) 122.0(10) C(104)-C(103)-C(102) 119.9(10) C(103)-C(104)-C(105) 120.3(10) C(90)#2-C(105)-C(106) 117.3(10) C(90)#2-C(105)-C(104) 127.1(11)
C(106)-C(105)-C(104) 115.4(10) N(21)-C(106)-N(18)#2 115.7(9) N(21)-C(106)-C(105) 123.6(10) N(18)#2-C(106)-C(105) 120.6(10) C(108)-C(107)-N(22) 123.3(11) C(107)-C(108)-C(109) 118.3(10) C(107)-C(108)-C(112) 120.6(12) C(109)-C(108)-C(112) 121.1(11) C(110)-C(109)-C(108) 117.5(11) C(109)-C(110)-C(111) 121.8(13) N(22)-C(111)-N(23) 115.9(10) N(22)-C(111)-C(110) 120.2(10) N(23)-C(111)-C(110) 123.2(12) C(113)-C(112)-C(117) 119.4(13) C(113)-C(112)-C(108) 120.8(14) C(117)-C(112)-C(108) 119.7(14) C(112)-C(113)-C(114) 122.9(15) C(115)-C(114)-C(113) 117.0(16) C(116)-C(115)-C(114) 121.2(15) C(115)-C(116)-C(117) 120.6(15) C(112)-C(117)-C(116) 118.2(15) N(23)-C(118)-N(24) 117.2(10) N(23)-C(118)-C(119) 124.7(11) N(24)-C(118)-C(119) 118.0(11) C(120)-C(119)-C(118) 120.2(11) C(119)-C(120)-C(121) 123.5(12) C(76)#2-C(121)-C(122) 115.3(11) C(76)#2-C(121)-C(120) 131.0(12) C(122)-C(121)-C(120) 113.4(12) N(24)-C(122)-N(15)#2 115.7(11) N(24)-C(122)-C(121) 122.9(11) N(15)#2-C(122)-C(121) 121.4(12) Cl(4)-C(123)-Cl(3) 110(2) Cl(5)-C(124)-Cl(6) 112.1(12) Cl(8)-C(125)-Cl(7) 113.7(12) Cl(9)-C(126)-Cl(10) 112.8(9) Cl(12)-C(127)-Cl(13) 58.5(18) Cl(12)-C(127)-Cl(11) 106(3)
186 Cl(13)-C(127)-Cl(11) 103(2)
F(6)-P(1)-F(3) 177.3(5)
F(7)-P(2)-F(10) 92.6(11) F(7)-P(2)-F(12) 174.1(10) F(10)-P(2)-F(12) 85.9(9)
F(7)-P(2)-F(11) 85.0(9)
F(10)-P(2)-F(11) 172.2(15) F(12)-P(2)-F(11) 97.2(11)
F(7)-P(2)-F(9) 86.7(9)
F(10)-P(2)-F(9) 90.1(9)
F(12)-P(2)-F(9) 87.5(11) F(11)-P(2)-F(9) 97.1(15)
F(7)-P(2)-F(8) 91.7(11)
F(10)-P(2)-F(8) 78.0(11)
F(12)-P(2)-F(8) 93.7(9)
F(11)-P(2)-F(8) 94.6(14)
F(9)-P(2)-F(8) 168.0(12)
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Symmetry transformations used to generate equivalent atoms:
#1 -x,y,-z+1/2 #2 -x+2,y,-z+1/2