科研之友
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摘要
Pyridyloxy cyclophosphazenes, spiro-N(3)P3(()O(2)C(12)H(8))(O-C5H4N-4)(4) (L1), dispiro-N3P3(O2C12H8)(2)(O-C5H4N-3)(2) (L2) and dispiro-N3P3(O2C12H8)(2)(O-C5H4N-(4))(2) (L3) were prepared and characterized. The crystal structure of L1 was determined which showed that the cyclophosphazene ring is planar. The reaction of L1 with anhydrous copper(II) chloride or silver nitrate afforded L2M4 metallamacrocycles [{L1}(2){ClCu(mu-Cl)(2)CuCl}](2)center dot 8CHCl3 (3) and[{L1}(2){(DMF)(0.5)(NO3)(0.5)Ag}(2){Ag(mu(2)-(O)NO2)(H2O)}(2)]{mu-[NO3]}center dot CH3OH (4) respectively. The molecular structure of 3 reveals that two CuCl2 dimers are bridged to each other in a complex metallamacrocycle that involves four metal ions and two ligands. The molecular structure of 4 is similar to that of 3 except for the presence of weak argentophilic interactions between the two Ag(I) centers. Also, a nitrate anion, which is trapped in the centre of the tetrameric assembly, assists in holding two Ag(I) ions together and 4 serves as a single source precursor for silver nanoparticles. The reaction L1 with ZnCl2 and Cd(NO3)(2)center dot 4H(2)O afforded the 1D-coordination polymers [{L-1}{ZnCl2}(2)]n center dot 2nCH(3)OH center dot 2nH(2)O (5) and [{L1} (2){Cd(CH3OH) 2(NO3) 2} 2{ Cd(NO3)(2)(H2O)}]n center dot 3nCH3OH center dot 3nH(2)O(6) respectively. While in 5 the 20-membered macrocycles are interconnected directly, in 6 they are bridged by a Cd(II) connector. The reaction of L2 with CoCl2 afforded the 1D-coordination polymer[{L2}2{CoCl2}]n2nCHCl3(7) which also contains interconnected 20-membered metallamacrocycles. On the other hand, the reaction of L2 with CuCl2 afforded [{L2} (2){ClCu( mu-Cl)}(2)]n center dot 2nCHCl3 center dot nH2O(8)which is a 1D-coordination polymer that contains{ClCu(mu-Cl)(2)CuCl}units. The reaction of L-3 with CuCl2 and Cd(NO3)(2)center dot 4H(2)O afforded[{L3}(2){CuCl2}]n center dot nDMF (9) and [{L-3} 2{Cd( NO3)(2)}]n center dot nCHCl(3)center dot nCH2Cl2 center dot nH2O (10) respectively. While 9 is a 2D-coordination polymer containing 48-membered metallamacrocycles, 10 is a 1D-coordination polymer containing interconnected 24-membered metallamacrocycles which possess spirocyclic cadmium ions as nodes.
- 出版日期2013
