Huang Yong-Qing, Shen Zhong-Liang, Okamura Taka-aki, Wang Yan, Wang Xiao-Feng, Sun Wei-Yin, Yu Jin-Quan, Ueyama Norikazu
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Dalton Trans. 2008 Jan 14(2):204-13. doi: 10.1039/b714502k. Epub 2007 Dec 4.
Seven new silver(I) complexes of the formula [Ag2(L)2(CF3SO3)2] (1), [Ag2(L)2(CH3SO3)2] (2) Ag2(L)22 (3), [Ag3(L)2(NO3)2]NO3.5H2O (4), [Ag2(L)(NO3)2].CH3OH (5), Ag2(L)22 (6) and Ag3(L)2(CH3CN)33 (7) have been synthesized by reactions of 1,3,5-tris(2-oxazolinyl)benzene (L) with varied silver(I) salts under different conditions. The influences of counter anions and reaction conditions on the structure of the complexes are discussed. Three complexes , 1, 2 and 3 with two kinds of different 1D chain structures were obtained under the same synthetic conditions by using different silver(I) salts, and the ligand L was found to adopt bis-monodentate (1 and 2) and tris-monodentate (3) coordination modes respectively. On the other hand, by using the same silver(I) nitrate or silver(I) perchlorate but different reaction solvents, 4 and 5 or 6 and 7 were isolated respectively. Complexes 4and 5 have different 1D chain structures, and 6 is isostructural with . However, 7 is a tri-nuclear, propeller-shaped M3L2 supramolecular capsule in which L adopts a cis,cis,cis-conformation, while the ligand L in 3-6 has cis,trans,trans-conformation. The results revealed that the nature of the counter anions, such as their size, coordination ability and coordination mode, and the reaction conditions all have great impact on the structure of the complexes. The complexes were also characterized by electrospray mass spectrometry. Furthermore, complex 7 exhibited modest second-harmonic-generation (SHG) efficiency.
通过1,3,5-三（2-恶唑啉基）苯（L）与不同的银（I）盐在不同条件下反应，合成了七种新的化学式为[Ag2(L)2(CF3SO3)2]（1）、[Ag2(L)2(CH3SO3)2]（2）、Ag2(L)22（3）、[Ag3(L)2(NO3)2]NO3·5H2O（4）、[Ag2(L)(NO3)2]·CH3OH（5）、Ag2(L)22（6）和Ag3(L)2(CH3CN)33（7）的银（I）配合物。讨论了抗衡阴离子和反应条件对配合物结构的影响。在相同的合成条件下，使用不同的银（I）盐得到了三种具有两种不同一维链结构的配合物1、2和3，发现配体L分别采用双单齿（1和2）和三单齿（3）配位模式。另一方面，使用相同的硝酸银（I）或高氯酸银（I）但不同的反应溶剂，分别分离得到了4和5或6和7。配合物4和5具有不同的一维链结构，6与……同构。然而，7是一种三核螺旋形M3L2超分子胶囊，其中L采用顺式、顺式、顺式构象，而3-6中的配体L具有顺式、反式、反式构象。结果表明，抗衡阴离子的性质，如它们的大小、配位能力和配位模式，以及反应条件都对配合物的结构有很大影响。这些配合物还通过电喷雾质谱进行了表征。此外，配合物7表现出适度的二次谐波产生（SHG）效率。
