TY - JOUR
T1 - Solvent-induced syntheses of 2D/3D [AgSCN] n-based supramolecular isomers with unusual topologies
T2 - Structural, theoretical and nonlinear optical studies
AU - Li, Jianghua
AU - Meng, Suci
AU - Zhang, Jinfang
AU - Song, Yinglin
AU - Huang, Zhipeng
AU - Zhao, Huajian
AU - Wei, Hongyang
AU - Huang, Wenjiang
AU - Cifuentes, Marie P.
AU - Humphrey, Mark G.
AU - Zhang, Chi
PY - 2012/4/21
Y1 - 2012/4/21
N2 - Reactions of hexamethylenetetramine (hmt) and AgSCN in different solvents generated three distinct [AgSCN] n-based coordination polymers (CPs): [Ag(1,3-μ 2-SCN)(μ 2-hmt)] n (1), {[Ag(1,1,3-μ 3-SCN)] 2(μ 2-hmt)} n (2) and [Ag(1,1,3-μ 3-SCN)(μ 4-hmt) 0.5] n (3). The identities of the coordination polymers (CPs) 1-3 have been unambiguously established by elemental analysis, IR, UV-vis spectra and single-crystal X-ray diffraction studies. Interestingly, 1 displays a two-dimensional (2D) (4,4) network involving one-dimensional (1D) zigzag [Ag(1,3-μ 2-SCN)] n chains bridged by μ 2-hmt linkers. 2 and 3 are novel 2D and three-dimensional (3D) supramolecular isomers: 2 presents an unusual 2D threaded-loop type (3,4)-connected {(3·4·5)(5 2·7)} {(3·4·5 3·6 3·7 2)(3·5 4·6 3·7 2)} network containing puckered [Ag(1,1,3-μ 3-SCN)] n networks linked by μ 2-hmt bridges, while 3 exhibits a unique 3D pillared-layer (3,4,6)-connected (4·6 2)(6 6) 2(4 2·6 10·8 3) framework in which the undulating [Ag(1,1,3-μ 3-SCN)] n layers are supported by μ 4-hmt pillars. 1-3 all possess good third-order nonlinear optical (NLO) properties. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations have afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.
AB - Reactions of hexamethylenetetramine (hmt) and AgSCN in different solvents generated three distinct [AgSCN] n-based coordination polymers (CPs): [Ag(1,3-μ 2-SCN)(μ 2-hmt)] n (1), {[Ag(1,1,3-μ 3-SCN)] 2(μ 2-hmt)} n (2) and [Ag(1,1,3-μ 3-SCN)(μ 4-hmt) 0.5] n (3). The identities of the coordination polymers (CPs) 1-3 have been unambiguously established by elemental analysis, IR, UV-vis spectra and single-crystal X-ray diffraction studies. Interestingly, 1 displays a two-dimensional (2D) (4,4) network involving one-dimensional (1D) zigzag [Ag(1,3-μ 2-SCN)] n chains bridged by μ 2-hmt linkers. 2 and 3 are novel 2D and three-dimensional (3D) supramolecular isomers: 2 presents an unusual 2D threaded-loop type (3,4)-connected {(3·4·5)(5 2·7)} {(3·4·5 3·6 3·7 2)(3·5 4·6 3·7 2)} network containing puckered [Ag(1,1,3-μ 3-SCN)] n networks linked by μ 2-hmt bridges, while 3 exhibits a unique 3D pillared-layer (3,4,6)-connected (4·6 2)(6 6) 2(4 2·6 10·8 3) framework in which the undulating [Ag(1,1,3-μ 3-SCN)] n layers are supported by μ 4-hmt pillars. 1-3 all possess good third-order nonlinear optical (NLO) properties. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations have afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.
UR - http://www.scopus.com/inward/record.url?scp=84860290273&partnerID=8YFLogxK
U2 - 10.1039/c2ce06610f
DO - 10.1039/c2ce06610f
M3 - Article
SN - 1466-8033
VL - 14
SP - 2787
EP - 2796
JO - CrystEngComm
JF - CrystEngComm
IS - 8
ER -