Novel Boxlike Dinuclear or Chain Polymeric Silver(I) Complexes with Polypyridyl Bridging Ligands: Syntheses, Crystal Structures, and Spectroscopic and Electrochemical Properties
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- 作者：Xian-He Bu ; He Liu ; Miao Du ; Keith Man-Chung Wong ; Vivian Wing-Wah Yam ; and Mitsuhiko Shionoya
- 刊名：Inorganic Chemistry
- 出版年：2001
- 出版时间：August 13, 2001
- 年：2001
- 卷：40
- 期：17
- 页码：4143 - 4149
- 全文大小：125K
- 年卷期：v.40,no.17(August 13, 2001)
- ISSN：1520-510X
文摘
The syntheses, characterization, crystal structures, and photophysical and electrochemical properties of two dinuclearand two polymeric AgI complexes with three polypyridyl ligands, 2,3-di-2-pyridylquinoxaline (L1), 2,3-di-2-pyridyl-5,8-dimethoxyquinoxaline (L2), and 2,3,7,8-tetrakis(2-pyridyl)pyrazino[2,3-g] quinoxaline (L3), aredescribed. The structures of the two boxlike dinuclear complexes with L1 and L2 and two chemically the samebut differently crystallized one-dimensional zigzag chain coordination polymers also consisting of boxlike dinuclearsubunits have been elucidated by X-ray analysis. [AgL1(CH3CN)]2-(BF4)2·2CHCl3 (1): monoclinic, C2/c; a =28.631(2), b = 12.2259(11), c = 14.3058(12) Å; 
= 99.180(2)
; Z = 4. [AgL2(CH3CN)2]2(ClO4)2 (2): triclinic,P
; a = 12.3398(2), b = 13.750(2), c = 14.326(7) Å; 
= 83.494(3), = 74.631(3), 
= 76.422(3); Z = 4.{[Ag2L3(NO3)2]·CH3CN}
(3a): monoclinic, P21/c; a = 9.5836(8), b = 13.4691(12), c = 14.0423(12) Å; =107.753(2); Z = 4. [Ag2L3(NO3)2] (3b): monoclinic, P21/c; a = 8.4689(6), b = 16.0447(12), c = 11.7307(8)Å; = 102.051(1); Z = 2. The structures of the dinuclear complexes 1 and 2 are similar to each other, with thetwo intramolecular AgI centers of each complex being spanned by two ligands thus forming a unique boxlikecyclic dimer. In 1, each AgI center is four-coordinated by three nitrogen atoms of two L1 ligands and a CH3CNnitrogen donor, taking a distorted tetrahedral coordination geometry. The coordination environment of AgI in 2is similar to that in 1, except the formation of an additional weak coordination bond with the oxygen atom of themethoxy group of L2. The structures of 3a,b are very similar to each other, except for the stacking patterns in thecrystal lattices, and the cyclic boxlike dinuclear unit, which is similar to the structure of 1, constitutes thefundamental building block to form the one-dimensional zigzag chain structures due to the "end-on" nature ofL3. 1-3 exhibit metal-perturbed intraligand transitions in solution in 360-390 nm regions. Cyclic voltammetricstudies of these complexes show the presence of reduction peak at ~-0.5 V vs Fc+/0. In the solid state at 77 K,they exhibit broad emission that may be assignable to originate from the metal-perturbed intraligand transitions.
= 99.180(2); Z = 4. [AgL2(CH3CN)2]2(ClO4)2 (2): triclinic,P; a = 12.3398(2), b = 13.750(2), c = 14.326(7) Å; = 83.494(3), = 74.631(3), = 76.422(3); Z = 4.{[Ag2L3(NO3)2]·CH3CN} (3a): monoclinic, P21/c; a = 9.5836(8), b = 13.4691(12), c = 14.0423(12) Å; =107.753(2); Z = 4. [Ag2L3(NO3)2] (3b): monoclinic, P21/c; a = 8.4689(6), b = 16.0447(12), c = 11.7307(8)Å; = 102.051(1); Z = 2. The structures of the dinuclear complexes 1 and 2 are similar to each other, with thetwo intramolecular AgI centers of each complex being spanned by two ligands thus forming a unique boxlikecyclic dimer. In 1, each AgI center is four-coordinated by three nitrogen atoms of two L1 ligands and a CH3CNnitrogen donor, taking a distorted tetrahedral coordination geometry. The coordination environment of AgI in 2is similar to that in 1, except the formation of an additional weak coordination bond with the oxygen atom of themethoxy group of L2. The structures of 3a,b are very similar to each other, except for the stacking patterns in thecrystal lattices, and the cyclic boxlike dinuclear unit, which is similar to the structure of 1, constitutes thefundamental building block to form the one-dimensional zigzag chain structures due to the "end-on" nature ofL3. 1-3 exhibit metal-perturbed intraligand transitions in solution in 360-390 nm regions. Cyclic voltammetricstudies of these complexes show the presence of reduction peak at ~-0.5 V vs Fc+/0. In the solid state at 77 K,they exhibit broad emission that may be assignable to originate from the metal-perturbed intraligand transitions.