[Cu2(µ-dppm2)(MeCN)2][BF4]2與含苯環的單羧酸 benzoic acid (BAc), o-toluic acid (oTAc), m-toluic acid (mTAc), p-toluic acid (pTAc), salicylic acid (Sac), 2-nitrobenzoic acid (2NBAc), 4-nitrobenzoic acid (4NBAc), 4-Phenylbutyric acid (4PBAc)及鄰, 間, 對苯二甲酸之雙羧酸 phthalic acid (PhAc), iso-phthalic acid (IsoPhAc), tere-phthalic acid (TerePhAc)反應形成 [Cu2(dppm)2(µ-BAc)](BF4) (1BF4), [Cu2(dppm)2(µ-oTAc)](BF4) (2BF4), [Cu2(dppm)2(µ-mTAc)](BF4) (3BF4), [Cu2(dppm)2(µ-pTAc)](BF4) (4BF4), [Cu2(dppm)2(µ-SAc)](BF4) (5BF4) , [Cu2(dppm)2(µ-4PBAc)](BF4) (6BF4), [Cu2(dppm)2(µ-2NBAc)](BF4) (7BF4), [Cu2(dppm)2(µ-4NBAc)](BF4) (8BF4), [{Cu2(dppm)2}2(µ-PhAc)](BF4)2 (9BF4)2 , [{Cu2(dppm)2}2(µ-IsoPhAc)](BF4)2 (10BF4)2 , [{Cu2(dppm)2}2(µ-TerephAc)](BF4)2 (11BF4)2
上述雙銅錯合物續與剛硬或柔軟的直線型雙芽含氮配位基N-N反應 (N-N = 4, 4’-bipyridyl (bipy) (a), 1, 2-bis (4-pyridyl)ethane (bpe) (b) , 1, 2-di (4-pyridyl)ethylene (dpe)(c), 4, 4’-trimethylenedipyridine (tmp) (d))形成多核銅錯合物，
包含寡聚物 {[Cu2(dppm)2(µ- BAc)]2(bpe)}(BF4)2, (1b(BF4) 2)
{[Cu2(dppm)2(µ-BAc)]2(dpe)}(BF4)2 (1c(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(dpe)}(BF4)2 (2c(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(bpe)}(BF4)2 (2b(BF4)2) ,
{[Cu2(dppm)2(µ-4PBAc)]2(bpe)}(BF4)2 (6b(BF4)2) ,
{[Cu2(dppm)2(µ-4NBAc)]2(bpe)}(BF4)2 (8b(BF4)2) ,
{[Cu2(dppm)2(µ-mTAc)]2(bpe)}(BF4)2 (3b(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(tmp)}(BF4)2 (2d(BF4)2) ,
{[Cu2(dppm)2(µ-pTAc)]2(tmp)}(BF4)2 (4d(BF4)2) , {[Cu2(dppm)2(µ-Sac)]2(bpe)}(BF4)2 (5b(BF4)2) , {[Cu2(dppm)2(µ-2NBAc)]2(bpe)}(BF4)2 (7b(BF4)2) , {[Cu2(dppm)2(µ-pTAc)]2(bpe)}(BF4)2 (4a(BF4)2) ,
{[Cu2(dppm)2(µ-2NBAc)]2(bipy)}(BF4)2 (7a(BF4)2) ,
{[Cu2(dppm)2(µ-pTAc)]2(bipy)}(BF4)2 (4a(BF4)2) ,
{[Cu2(dppm)2}2(µ-PhAc)2(bipy)}(BF4)4 (9a(BF4)4) ,
聚合物 [Cu2(dppm)2(µ-2NBAc)(tmp)]n(BF4)n (7d(BF4)n) ,
[Cu2(dppm)2(µ-BAc)(bipy)]n(BF4)n (1a(BF4)n) ,
[{Cu2(dppm)2}2(µ-PhAc)(bpe)]n(BF4)2n (9b(BF4)2n) ,
[{Cu2(dppm)2}2(µ-(PhAc)(tmp)]n(BF4)2n (9d(BF4)2n) ,
[{Cu2(dppm)2}2(µ-(IsoPhAc)(bipy)]n(BF4)2n (10a(BF4)2n)以及不規則金屬環 [{Cu2(dppm)2}2(µ-IsoPhAc)(bpe)](BF4)2 (10b(BF4)2) , [{Cu2(dppm)2}2(µ-IsoPhAc)(tmp)](BF4)2 (10d(BF4)2) 及長方形金屬環 {[[Cu2(dppm)2]2(µ-TerePhAc)]2(bpe)2}(BF4)4 (11b(BF4)4)
等結構。所有的錯合物，利用NMR、EA、IR、ESI-MS鑑定其性質，並且由X-ray data 得到固態結構。
藉由光譜及質譜的證據證明組成不同的超分子產物在溶劑中存在快速動力交換現象。[Cu2(dppm)2(µ-BAc)](BF4) 與tmp反應可以形成不同結構 [[Cu2(dppm)2(µ-BAc)]2(tmp)](BF4)2 (1d(BF4)2) 及 [{Cu2(dppm)2}(µ- BAc)(tmp)]n(BF4)n (1d(BF4)n)。

[Cu2(µ-dppm2)(MeCN)2][BF4]2 reacted with benzoic acid (BAc), o-toluic acid (oTAc), m-toluic acid (mTAc), p-toluic acid (pTAc), salicylic acid (Sac) , 2-nitrobenzoic acid (2NBAc), 4-nitrobenzoic acid (4NBAc), 4-Phenylbutyric acid (4PBAc), phthalic acid (PhAc), iso-phthalic acid (IsoPhAc), tere-phthalic acid (TerePhAc) to produced [Cu2(dppm)2(µ- BAc)](BF4) (1BF4), [Cu2(dppm)2(µ- oTAc)](BF4) (2BF4), [Cu2(dppm)2(µ- mTAc)](BF4) (3BF4), [Cu2(dppm)2(µ-p TAc)](BF4) (4BF4), [Cu2(dppm)2(µ-SAc)](BF4) (5BF4), [Cu2(dppm)2(µ-4PBAc)](BF4) (6BF4) , [Cu2(dppm)2(µ-2NBAc)](BF4) (7BF4) , [Cu2(dppm)2(µ-4NBAc)](BF4) (8BF4) , [{Cu2(dppm)2}2(µ-PhAc)](BF4)2 (9BF4)2 , [{Cu2(dppm)2}2(µ-IsoPhAc)](BF4)2 (10BF4)2 and[{Cu2(dppm)2}2(µ-TerephAc)] (BF4)2 (11BF4)2
then reacted with rigid or flexible linear bidentate donors, (N-N = 4, 4’-bipyridyl (bipy) (a), 1, 2-bis (4-pyridyl)ethane (bpe) (b) , 1, 2-di (4-pyridyl)ethylene (dpe)(c), 4, 4’-trimethylenedipyridine (tmp) (d)) , respectively . Twenty four compounds are formed，
including : oligomer{[Cu2(dppm)2(µ-BAc)]2(bpe)}(BF4)2 (1b(BF4)2) , {[Cu2(dppm)2(µ-BAc)]2(dpe)}(BF4)2 (1c(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(dpe)}(BF4)2 (2c(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(bpe)}(BF4)2 (2b(BF4)2) ,
{[Cu2(dppm)2(µ-4PBAc)]2(bpe)}(BF4)2 (6b(BF4)2) ,
{[Cu2(dppm)2(µ-4NBAc)]2(bpe)}(BF4)2 (8b(BF4)2) ,
{[Cu2(dppm)2(µ-mTAc)]2(bpe)}(BF4)2 (3b(BF4)2) ,
{[Cu2(dppm)2(µ-oTAc)]2(tmp)}(BF4)2 (2d(BF4)2) ,
{[Cu2(dppm)2(µ-pTAc)]2(tmp)}(BF4)2 (4d(BF4)2) , {[Cu2(dppm)2(µ-Sac)]2(bpe)}(BF4)2 (5b(BF4)2) , {[Cu2(dppm)2(µ-2NBAc)]2(bpe)}(BF4)2 (7b(BF4)2) , {[Cu2(dppm)2(µ-pTAc)]2(bpe)}(BF4)2 (4a(BF4)2) ,
{[Cu2(dppm)2(µ-2NBAc)]2(bipy)}(BF4)2 (7a(BF4)2) ,
{[Cu2(dppm)2(µ-pTAc)]2(bipy)}(BF4)2 (4a(BF4)2) ,
{[Cu2(dppm)2}2(µ-PhAc)2(bipy)}(BF4)4 (9a(BF4)4) ,
polymer[Cu2(dppm)2(µ-2NBAc)(tmp)]n(BF4)n (7d(BF4)n) ,
[Cu2(dppm)2(µ- BAc)(bipy)]n(BF4)n (b(BF4)n) ,
[{Cu2(dppm)2}2(µ-PhAc)(bpe)]n(BF4)2n (9b(BF4)2n) ,
[{Cu2(dppm)2}2(µ-(PhAc)(tmp)]n(BF4)2n (9d(BF4)2n) ,
[{Cu2(dppm)2}2(µ-(IsoPhAc)(bipy)]n(BF4)2n (10a(BF4)2n) , irregular metallacycles [{Cu2(dppm)2}2(µ-IsoPhAc)(bpe)](BF4)2 (10b(BF4)2) , [{Cu2(dppm)2}2(µ-IsoPhAc)(tmp)](BF4)2 (10d(BF4) 2) and a rectangle
metallacyle {[[Cu2(dppm)2]2(µ-TerePhAc)]2(bpe)2}(BF4)4 (11b(BF4)4) .
All complexes were characterized by elemental analyses、 NMR 、ESI-MS and IR spectra . Single-crystal structures of each complex were also determined by X-ray single-crystal diffraction data.
Interestingly, in solution, both spectral and MS evidences for some
adducts show that rapid dynamic exchange exists between different supramolecules.Truly, one complex can form two different structures [[Cu2(dppm)2(µ- BAc)]2(tmp)](BF4) (1d(BF4)2) and [{Cu2(dppm)2}(µ- BAc)(tmp)]n(BF4)n (1d(BF4)n)。

1. Steed, J.W.; Atwood,J.L.Supramolecular Chemistry; Wiley, New York, 2000; p19-30
2.Lehn, J.-M. Chem. Soc. Rev., 2007, 36, 151
3. Hasenknopf,L. ; Lehn ,J.-M. ; Boumediene, N. ; Annick, D.G, ; Dorsselaer , A. V; Kneisel, B.; Fenske, D. J. Am. Chem. Soc. 1997, 119, 10956
4.Sreenivasachary, N.; Lehn, J.-M., Proc. Natl. Acad. Sci. U. S. A., 2005, 102, 5938.
5. Giuseppone,N.; Schmitt; J.L.; Lehn, J.-M., Angew. Chem., Int. Ed., 2004, 43, 4902.
6. Giuseppone,N.; Lehn, J.-M, J. Am.Chem. Soc., 2004, 126, 11448.
7. Lehn, J.-M. Chem.–Eur. J., 1999, 5, 2455
8. (a) Ramstro¨M,O.; Lehn,J.-M. Nat. Rev. Drug Discovery, 2002, 1, 26; (b) Hochgu¨ rtel, M.; Lehn, J.-M. Fragmentbased
Approaches in Drug Discovery, Wiley-VCH, Weinheim, 2006, ch. 16.
9. Fujita, M.; Sasaki, P.O; Mitsuhashi, T.; Fujita, T.; Yazaki, J.;Ogura, K. Chem.Soc.,Chem. Commun., 1996, 1535
10. Fujita, M. ; Yazaki, J.; Ogura, K. J. Am. Chem. Soc., 1990, 112,5645;
11. Josefina Diez; M. Gamasa, P.; Gimeno, J. J. Chem. Soc. Dalton Trans. 1987 1275
12. Mo; J. Hu; G.Z.; Chen,W.; Li.Y; Pan , A.S. Acta Cryst. (2008). E64, m391
13. Jin, Q.-H.; Chen, L.-M. ; Li,P.-Z.; Deng, S.-F.; Wang,R. Inorganica Chimica Acta 2009 362 5224
14. Gan. Acta Crystallogr. Sect. E. 2009, 65, 358
15. Fu. Polyhedron 2008, 27, 2202
16. Shiu, K.-B.; Liu, S.-A.; Lee, G.-H. Inorg. Chem. 2010, 49, 9902
17. Teo, P.;Koh, L.-L.; Hor, T.S.S.A. Inorg.Chem.2008,47,6464
18. Chakrabarty, R.; Mukherjee, P.S.; Stang,P.J. Chem. Rev. 2011, 111, 6810
19. Harvey, P.D.;Drouin, M.; Zhang, T. Inorg. Chem. 1997, 36, 4998
20. Wheaton, C.A.; Jennings, M.C.; and Puddephatt, R.J. J. Am. Chem. Soc. 2006, 128, 15370
21. Pedersen, C.J. J. Am.Chem. Soc., 1967, 89, 7017.
22. Janiak, C, J. Chem. Soc., Dalton Trans., 2000,3885.
23. Petitjean,A., Lehn,J.M. J. Am. Chem. Soc. 2004, 126, 6637