系列钴配合物的合成、结构及自旋转换现象的探索
摘要
采用常规和非常规方法合成了5种含过渡金属钴的配合物，得到了它们的
单晶体，经X光四圆衍射测定并确定了它们的结构，其分子式如下：
（1）Co（Imh）_6（NO_3）_2
（2）[Co（phen）_2（H_2O）]_2（tpha）｝（NO_3）_2·2C_2H_5OH
（3）[Co（NH_2NHCSNH_2）_3][Cr（ox）_3]·6H_2O
（4）Co（NH_2NHCSNH_2）_3Cl_3·1/2HCl
（5）[Et_4N][Co（NH_2NHCSNH_2）_3][Mo_8O_(26)]·4Me_2NCHO
采用降温、升温和微波反应等实验手段，对上述5种化合物及其它一些含
不同配位原子（N，O，S，P，Cl）的系列钴配合物进行了自旋转换现象的捕捉实验。
发现全N配位、全O配位或N，O配位的钴配合物对自旋转换都十分有利。
它们在实验过程中有较为明显的颜色变化和很好的可逆性，表明这些配合物自
旋转换性能的存在。
特别是对化合物（2）和（3）进行了变温磁性研究，发现化合物（2）在
低温下10K～100K之间存在着明显的两步自旋转换，并对此进行了理论分析和
解释。
此外，还研究了以上5种配合物的IR，UV-VIS-NIR等谱学性质，为进一步
确认结构和发现新性质提供了证据。
关于具有自旋转换性能的Co~(n+)（n=2，3）配合物的研究，只是近1～2年内在
国际上才刚刚开始的。但这些化合物已经表现出了比Fe~(2+)（Fe~(3+)）化合物更为奇
特的性质和功能，这对于记忆、存储等新型分子基功能材料的开阔研究有重要
意义。
Taking the regular and irregular methods , five new cobalt compounds containing transition metal have been synthesized and characterized by single-crystal X-ray four-circle diffraction. Their formulas are presented as following:
(1) Co(Imh)6(N03)2
(2) { [Co(~jphen)2(H2Q)]2(tpha) } (N03)2.2C2H50H
(3) [Co(NH2NHCSNH2)3] [Cr(ox)3].6H20
(4) Co(NH2NHCSNH2)3Cl3. 1/2HC1
(5) [Et4N] [ Co(NH2NHCSNH2)3] [Mo8026] ?Me2NCHO
The phenomenon of spin tranistion has been found for above five compounds and series of cobalt compounds containing different coordinated atoms (N,O,S,P,Cl) by decreasing temperature increasing temperature and microwave reaction. Those cobalt complexes which coordinated by all nitrogen atoms and all oxygen atoms or their combination show a positive tendency to spin transition. All of them exhibit pronounced color change and reversibility, which show the occurrence of spin transition.
In particular, we find compound (2) show pronounced spin transition in the range of 1 OKA 00K by variable-temperature magnetic susceptibility measurements for compound (2) and compound (3) , and a theoretical analysis and explanation is done according to this.
In addition, these five compounds have been characterized by IR,UV-VIS-NIR spectroscopes,which provide more evidence for determining their structure and exploring their new properties.
The investigation of spin transition in cobalt compounds has just begun in recent two years, but they has shown more unique properties and function than iron compounds. It has more important significance for the further study of new-type molecular-based materials.
单晶体，经X光四圆衍射测定并确定了它们的结构，其分子式如下：
（1）Co（Imh）_6（NO_3）_2
（2）[Co（phen）_2（H_2O）]_2（tpha）｝（NO_3）_2·2C_2H_5OH
（3）[Co（NH_2NHCSNH_2）_3][Cr（ox）_3]·6H_2O
（4）Co（NH_2NHCSNH_2）_3Cl_3·1/2HCl
（5）[Et_4N][Co（NH_2NHCSNH_2）_3][Mo_8O_(26)]·4Me_2NCHO
采用降温、升温和微波反应等实验手段，对上述5种化合物及其它一些含
不同配位原子（N，O，S，P，Cl）的系列钴配合物进行了自旋转换现象的捕捉实验。
发现全N配位、全O配位或N，O配位的钴配合物对自旋转换都十分有利。
它们在实验过程中有较为明显的颜色变化和很好的可逆性，表明这些配合物自
旋转换性能的存在。
特别是对化合物（2）和（3）进行了变温磁性研究，发现化合物（2）在
低温下10K～100K之间存在着明显的两步自旋转换，并对此进行了理论分析和
解释。
此外，还研究了以上5种配合物的IR，UV-VIS-NIR等谱学性质，为进一步
确认结构和发现新性质提供了证据。
关于具有自旋转换性能的Co~(n+)（n=2，3）配合物的研究，只是近1～2年内在
国际上才刚刚开始的。但这些化合物已经表现出了比Fe~(2+)（Fe~(3+)）化合物更为奇
特的性质和功能，这对于记忆、存储等新型分子基功能材料的开阔研究有重要
意义。
Taking the regular and irregular methods , five new cobalt compounds containing transition metal have been synthesized and characterized by single-crystal X-ray four-circle diffraction. Their formulas are presented as following:
(1) Co(Imh)6(N03)2
(2) { [Co(~jphen)2(H2Q)]2(tpha) } (N03)2.2C2H50H
(3) [Co(NH2NHCSNH2)3] [Cr(ox)3].6H20
(4) Co(NH2NHCSNH2)3Cl3. 1/2HC1
(5) [Et4N] [ Co(NH2NHCSNH2)3] [Mo8026] ?Me2NCHO
The phenomenon of spin tranistion has been found for above five compounds and series of cobalt compounds containing different coordinated atoms (N,O,S,P,Cl) by decreasing temperature increasing temperature and microwave reaction. Those cobalt complexes which coordinated by all nitrogen atoms and all oxygen atoms or their combination show a positive tendency to spin transition. All of them exhibit pronounced color change and reversibility, which show the occurrence of spin transition.
In particular, we find compound (2) show pronounced spin transition in the range of 1 OKA 00K by variable-temperature magnetic susceptibility measurements for compound (2) and compound (3) , and a theoretical analysis and explanation is done according to this.
In addition, these five compounds have been characterized by IR,UV-VIS-NIR spectroscopes,which provide more evidence for determining their structure and exploring their new properties.
The investigation of spin transition in cobalt compounds has just begun in recent two years, but they has shown more unique properties and function than iron compounds. It has more important significance for the further study of new-type molecular-based materials.
引文
1. Kahn O, Martinz C J, Science, 1998, 279(2): 44-48.
2．王红梅，廖代正，大学化学，1997，12(4)：10-13．
3．王红梅，廖代正，化学通报，1997，10：22-28．
4．王红梅，李立存，杨光明等，高等学校化学学报，1993，19(7)：1020—1022．
5．王红梅，刘欣，李立存等，化学通报，2000，58(1)：39-42．
6. Héléne Soyer, Elaine Dupart et al., Advanced Materials, 1999,11 (5):382-38.
7. Jean Francosis Letard, Oliver Kahn et al., Inorg. Chem.,1999,38:3020-3021.
8. Vreugdenhil W, Diemenj H V, Graaffra G D et al. Polyhedron, 1990, 9(24); 2971-2979.
9. Garcia Y, Kahn O, Rabardel L et al., Inorg. Chem., 1999, 38(21): 4663-4670.
10. Letard J F, Cuionneau P, Rabardel L et al., Inorg. Chem., 1998, 37(17): 4432-4441.
11. Letard J F, Guionneau P, Codjovie E, et al., J. Am. Chem. Soc., 1997, 119 (44): 10861-10862.
12. Matouzenko G S, Bousseksou A, Lecocqs et al., Inorg. Chem., 1997, 36(25):5869-5879.
13. Nicolas Moliner, M.Carmen Munoz,et al., Inorganic.Chimica Acta, 1999,291:279-288
14. Kahn O, Molecular Magnetism, VCH, New york, 1993.
15. Peble J.,Inorg. Chem., 1983,22:4125-4128.
16. Decurtins S,Gutlich P, Kohler C P. et al., Chem. Phys.lett, 1984,105:1-4.
17. Hauser A.et al.,Chem. Phys. Lett, 1986,124:543-548.
18. Glichter P, Drickemer H G.,J.Chem. Phys., 1972,56:2142-2146.
19. Sugiyarto K H, Craig D C, Rae A D et al., J.Chem.,1995,48:35-54.
20. Gallois B, Real J A, Hauw C et al., Inorg. Chem.,1990,29:1152-1158.
21. Zhong, Z. J. Tao, J.Q. et al., J. Chem. Soc. Datlon Trans.,1998,327.
22. Gutlich. P., Hauser. A., Coord. Chem. Rev.,1990,97:1.
23. Wiehl.L. Acta Crystallogr, 1993, B 49,289.
24. Franke.P.L., Haasnoot. J.G.,et al., Inorg Chim Acta,1982,59:5.
25. Muller. W.E.; Ensling. J.,et al., Inorg. Chem. 1983,22,2074.
26. Kahn. O, Krober J, Jay C., Adv. Mater, 1992,4:718-727.
27. Lavrenove, L.G.; Ikorskii, N.V. et al., Koord. Khim., 1990,16:654.
28. L.G.Lavrenove,et al., Koordinationaya Khimiya, 1986,12:207.
29. P. Stupik, J.H.Zhang et al., Hyperfine Interact., 1986,28:725.
30. Andrzej Ozarowski,Yu Shun Zhong et al., Inorg. Chem, 1991,30:3167-3174.
31． S.Decurtins, P.Gutlich et al.,Inorg.Chem.,1985 ,24:2174．
32． A.Hauser, P.Gutlich et al., Inorg.Chem, 1996,25:4245．
33． A Hauser, Coord.Chem.Rev,1991,111:275．
34． PAdler, P.Poganiuch et al. Hyperfine Interactions ,1989,52:47．
35． P.Poganiuch, S. Decurtins et al. J.Am.Chem.Soc, 1990,112:3270．
36． P.Gutlich and P.Poganiuch et al.,Ed.Engl ,1991,30:975．
37． Van Koningsbruggen,Oliver Kahn et al.,Inorg.Chem.,2000,39:1891-1990．
38． W.Linert,M.Konecny and F.Renz ,J.Chem.Soc.Dalton Trans., 1994,1523．
39． O.Kahn, Molecular Magnetism, p.67． VCH, New York(1993) .
40． Buchen,T.;Gutlich,P.et al .Chem.Eur.J.1996,2,No.9,1134．
41． Goodwin, H. A.et al.,Chem. Phys.Lett., 1987,139,470．
42． Th.Buchen,P.Gutlich et al.,Inorg.Chem.,1994,33,4573-4576．
43． Raymond C.W.Sung and Bruce R.McGarvey, Inorg.Chem, 1999,38:3644-3650．
44． Roman Boca, Peter Baran et al., Polyhedron vol.16, No.1, pp 47-55,1997．
45． Matouzenko, G. S.; Bousseksou, A. et al., Inorg.Chem ,1997,36:2975．
46． Harald Romstedt, Andreas Hauser et al., J.Phys.Chem.Solids. vol. 59,No.2,pp 265-275,1998．
47． C.P., Kohler, R. Jakovi et al., J.Phys.Chem.Solids, vol.51, No.3, pp239-247,1990．
48． Herve Daubric, Christophe Cantin et al., Chemical Physics ,1999,244,75-88．
49． Michio Sorai, et al., J.Phys.Chem.Solids, Vol.51, No.8, pp941-951, 1990．
50． Jean-Francois Letard,.Philippe Guionneau et al., J.Am.Chem, 1997,119:10861-10862．
51． Jean-Francois Letard, Philippe Guionneau et al., Inorg.Chem, 1998,37:4432-4441．
52． Galina S.,Matouzenko,Azzedine Bousseksou et al., Inorg.Chem.,1997,36:5869-5879．
53． Renee Claude, Jose-Antonio Real et al., Inorg.Chem.,1990,29:4442-4448．
54． Jean-Francois Letard, Jose Antonio Real et al., J.Am.Chem.Soc.,1999,121:10630-10631．
55． Jose Antonio Real, Isabel Castro et al.,Inorg.Chem.,1997,36:455-464．
56． C.P.Kohler, R.Jakobi et al., J.Phys.Chem.Solids, vol 51,No.3,pp239-247,1980．
57． Nicolas Moliner, Jose Antonio Real et al., J.Chem.Soc.Dalton Trans.,1999,1375-1379．
58． Alin Diebold and Karl S.Hagen, Inorg.Chem.,1998,37:215-223．
59． Peter E.Doan and Bruce R.Mc Garvey, Inorg.Chem., 1990,29,874-876．
60． Jean Francois Letard, Oliver Kahn et al., Inorg.Chem.,1999,38:3020-3021．
61． Rolfe H. Herber et al., Inorg.Chem.,1987,26:173-178．
62． I.Sanner,E-Meissner et al.,Chemical Physics.,1984,86:227-233．
63． Jakobi,R.,Spiering,H.et al., J.Phys.Chem.Solids.,1992,53:267．
64． Harald Romstedt, Andreas Hauser et al., J.Phy.Chem.Solids.,vol 59,No.2pp265-275,1998．
65． Gerg Brewer,Jerry Jasinski et al., Inorganica Chimica Acta .1995,232:183-187．
66． E.T.Kimtmer and J.H.Dawson., Inorg.Chem.,199130:4892．
67． J.P.Fitzgerald,B.S.Haggerty et al., Inorg.Chem.,1992,31:2006．
68． Michio Sorai, Yatsuhisa Nagano et al., J.Phys.Chem.Solids., vol55,No.4,pp317-326,1994．
69． Mohan M.Bhadbhade and D.srinivas., Polyhedron , vol 17,Nol6,pp2699-2711,1998．
70． Shigeeyuki Hirose,Shinya Hayami et al., Bull.Chem.Soc.Jpn.,2000,73:2059-2066．
71． Rita Hernandez-Molina,Alfredo Mederos et al., Inorg.Chem.,1998,37:5102-5108．
72． Ana Maria Josceanu andPeter Moore., J.Chem.Soc.Dalton Trans.,1998,369-374．
73． Andrew J.Conti,Kazutoshi Kaji et al., Inorg Chem.,1993,32:2681-2693．
74． C.Roux,J.Zarembowitch et al., Inorg.Chem.,1994,33:2273．
75． J..Zarembowitch,M.L.Boillot et al., Inorg.Chem.,1996,35:3975．
76． Jose Antonio Real,M.Carmen Munoz et al., Inorg.Chem.,1994,33:3587-3594．
77． Nicolas Moliner,M.Carmen Munoz et al., Inorganica Chimica Acta, 1998,274:1-6．
78． David W.Blakesey,Sonha C.Payne.et at., Inorg.Chem.,2000,39:1979-1989．
79． Thierry Granier,Bernard Gallois et al.,Inorg.Chem.,1993,32:5305-5312．
80． Ren-Gen Xiong,Scoot R.Wilson and wenbin Lin .,J.Chem.Soc.Dalton Trans., 1998,4089-4090．
81． Katja Heinze,Gottfried Huttner et al., Inorg.Chem., 1997,36:5457-5469．
82． Rodolphe Clerac,F.Alver Cotton,et al., J.Am.Chem.Soc.,2000,122:2272-2278．
83． Balbir Chand Verma and Shashi Bala Kali A., Polyhedron,voll4,No.23-24,pp3549-3556,1995．
84． Juciusz A.Wolny,Mikolaj F.Rudolf et al., J.Chem.Soc.Dalton Trans.,1993,1611-162．
85． Konig, Inorganic Chem.Vol. 8, 1969, 1280．
86． Kolks, G., Lippard ,S.J., Waszczak, J. V. et al., J.Am.Chem.Soc., 1982,104:717．
87． Kahn O. Angew Chem Int Ed Engl, 1985,24:834．
88． Kahn O. Inorg Chem Acta, 1982,62:3．
2．王红梅，廖代正，大学化学，1997，12(4)：10-13．
3．王红梅，廖代正，化学通报，1997，10：22-28．
4．王红梅，李立存，杨光明等，高等学校化学学报，1993，19(7)：1020—1022．
5．王红梅，刘欣，李立存等，化学通报，2000，58(1)：39-42．
6. Héléne Soyer, Elaine Dupart et al., Advanced Materials, 1999,11 (5):382-38.
7. Jean Francosis Letard, Oliver Kahn et al., Inorg. Chem.,1999,38:3020-3021.
8. Vreugdenhil W, Diemenj H V, Graaffra G D et al. Polyhedron, 1990, 9(24); 2971-2979.
9. Garcia Y, Kahn O, Rabardel L et al., Inorg. Chem., 1999, 38(21): 4663-4670.
10. Letard J F, Cuionneau P, Rabardel L et al., Inorg. Chem., 1998, 37(17): 4432-4441.
11. Letard J F, Guionneau P, Codjovie E, et al., J. Am. Chem. Soc., 1997, 119 (44): 10861-10862.
12. Matouzenko G S, Bousseksou A, Lecocqs et al., Inorg. Chem., 1997, 36(25):5869-5879.
13. Nicolas Moliner, M.Carmen Munoz,et al., Inorganic.Chimica Acta, 1999,291:279-288
14. Kahn O, Molecular Magnetism, VCH, New york, 1993.
15. Peble J.,Inorg. Chem., 1983,22:4125-4128.
16. Decurtins S,Gutlich P, Kohler C P. et al., Chem. Phys.lett, 1984,105:1-4.
17. Hauser A.et al.,Chem. Phys. Lett, 1986,124:543-548.
18. Glichter P, Drickemer H G.,J.Chem. Phys., 1972,56:2142-2146.
19. Sugiyarto K H, Craig D C, Rae A D et al., J.Chem.,1995,48:35-54.
20. Gallois B, Real J A, Hauw C et al., Inorg. Chem.,1990,29:1152-1158.
21. Zhong, Z. J. Tao, J.Q. et al., J. Chem. Soc. Datlon Trans.,1998,327.
22. Gutlich. P., Hauser. A., Coord. Chem. Rev.,1990,97:1.
23. Wiehl.L. Acta Crystallogr, 1993, B 49,289.
24. Franke.P.L., Haasnoot. J.G.,et al., Inorg Chim Acta,1982,59:5.
25. Muller. W.E.; Ensling. J.,et al., Inorg. Chem. 1983,22,2074.
26. Kahn. O, Krober J, Jay C., Adv. Mater, 1992,4:718-727.
27. Lavrenove, L.G.; Ikorskii, N.V. et al., Koord. Khim., 1990,16:654.
28. L.G.Lavrenove,et al., Koordinationaya Khimiya, 1986,12:207.
29. P. Stupik, J.H.Zhang et al., Hyperfine Interact., 1986,28:725.
30. Andrzej Ozarowski,Yu Shun Zhong et al., Inorg. Chem, 1991,30:3167-3174.
31． S.Decurtins, P.Gutlich et al.,Inorg.Chem.,1985 ,24:2174．
32． A.Hauser, P.Gutlich et al., Inorg.Chem, 1996,25:4245．
33． A Hauser, Coord.Chem.Rev,1991,111:275．
34． PAdler, P.Poganiuch et al. Hyperfine Interactions ,1989,52:47．
35． P.Poganiuch, S. Decurtins et al. J.Am.Chem.Soc, 1990,112:3270．
36． P.Gutlich and P.Poganiuch et al.,Ed.Engl ,1991,30:975．
37． Van Koningsbruggen,Oliver Kahn et al.,Inorg.Chem.,2000,39:1891-1990．
38． W.Linert,M.Konecny and F.Renz ,J.Chem.Soc.Dalton Trans., 1994,1523．
39． O.Kahn, Molecular Magnetism, p.67． VCH, New York(1993) .
40． Buchen,T.;Gutlich,P.et al .Chem.Eur.J.1996,2,No.9,1134．
41． Goodwin, H. A.et al.,Chem. Phys.Lett., 1987,139,470．
42． Th.Buchen,P.Gutlich et al.,Inorg.Chem.,1994,33,4573-4576．
43． Raymond C.W.Sung and Bruce R.McGarvey, Inorg.Chem, 1999,38:3644-3650．
44． Roman Boca, Peter Baran et al., Polyhedron vol.16, No.1, pp 47-55,1997．
45． Matouzenko, G. S.; Bousseksou, A. et al., Inorg.Chem ,1997,36:2975．
46． Harald Romstedt, Andreas Hauser et al., J.Phys.Chem.Solids. vol. 59,No.2,pp 265-275,1998．
47． C.P., Kohler, R. Jakovi et al., J.Phys.Chem.Solids, vol.51, No.3, pp239-247,1990．
48． Herve Daubric, Christophe Cantin et al., Chemical Physics ,1999,244,75-88．
49． Michio Sorai, et al., J.Phys.Chem.Solids, Vol.51, No.8, pp941-951, 1990．
50． Jean-Francois Letard,.Philippe Guionneau et al., J.Am.Chem, 1997,119:10861-10862．
51． Jean-Francois Letard, Philippe Guionneau et al., Inorg.Chem, 1998,37:4432-4441．
52． Galina S.,Matouzenko,Azzedine Bousseksou et al., Inorg.Chem.,1997,36:5869-5879．
53． Renee Claude, Jose-Antonio Real et al., Inorg.Chem.,1990,29:4442-4448．
54． Jean-Francois Letard, Jose Antonio Real et al., J.Am.Chem.Soc.,1999,121:10630-10631．
55． Jose Antonio Real, Isabel Castro et al.,Inorg.Chem.,1997,36:455-464．
56． C.P.Kohler, R.Jakobi et al., J.Phys.Chem.Solids, vol 51,No.3,pp239-247,1980．
57． Nicolas Moliner, Jose Antonio Real et al., J.Chem.Soc.Dalton Trans.,1999,1375-1379．
58． Alin Diebold and Karl S.Hagen, Inorg.Chem.,1998,37:215-223．
59． Peter E.Doan and Bruce R.Mc Garvey, Inorg.Chem., 1990,29,874-876．
60． Jean Francois Letard, Oliver Kahn et al., Inorg.Chem.,1999,38:3020-3021．
61． Rolfe H. Herber et al., Inorg.Chem.,1987,26:173-178．
62． I.Sanner,E-Meissner et al.,Chemical Physics.,1984,86:227-233．
63． Jakobi,R.,Spiering,H.et al., J.Phys.Chem.Solids.,1992,53:267．
64． Harald Romstedt, Andreas Hauser et al., J.Phy.Chem.Solids.,vol 59,No.2pp265-275,1998．
65． Gerg Brewer,Jerry Jasinski et al., Inorganica Chimica Acta .1995,232:183-187．
66． E.T.Kimtmer and J.H.Dawson., Inorg.Chem.,199130:4892．
67． J.P.Fitzgerald,B.S.Haggerty et al., Inorg.Chem.,1992,31:2006．
68． Michio Sorai, Yatsuhisa Nagano et al., J.Phys.Chem.Solids., vol55,No.4,pp317-326,1994．
69． Mohan M.Bhadbhade and D.srinivas., Polyhedron , vol 17,Nol6,pp2699-2711,1998．
70． Shigeeyuki Hirose,Shinya Hayami et al., Bull.Chem.Soc.Jpn.,2000,73:2059-2066．
71． Rita Hernandez-Molina,Alfredo Mederos et al., Inorg.Chem.,1998,37:5102-5108．
72． Ana Maria Josceanu andPeter Moore., J.Chem.Soc.Dalton Trans.,1998,369-374．
73． Andrew J.Conti,Kazutoshi Kaji et al., Inorg Chem.,1993,32:2681-2693．
74． C.Roux,J.Zarembowitch et al., Inorg.Chem.,1994,33:2273．
75． J..Zarembowitch,M.L.Boillot et al., Inorg.Chem.,1996,35:3975．
76． Jose Antonio Real,M.Carmen Munoz et al., Inorg.Chem.,1994,33:3587-3594．
77． Nicolas Moliner,M.Carmen Munoz et al., Inorganica Chimica Acta, 1998,274:1-6．
78． David W.Blakesey,Sonha C.Payne.et at., Inorg.Chem.,2000,39:1979-1989．
79． Thierry Granier,Bernard Gallois et al.,Inorg.Chem.,1993,32:5305-5312．
80． Ren-Gen Xiong,Scoot R.Wilson and wenbin Lin .,J.Chem.Soc.Dalton Trans., 1998,4089-4090．
81． Katja Heinze,Gottfried Huttner et al., Inorg.Chem., 1997,36:5457-5469．
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