Synthesis, characterization, and calculated electronic structure of the crystalline metal-organic polymers [Hg(SC6H4S)(en)]n and [Pb(SC6H4S)(dien)]n.
作者： Dayna L. Turner , Kevin H. Stone , Peter W. Stephens , Aron Walsh , Mayank Pratap Singh
DOI: 10.1021/IC201779A
关键词: Metal 、 Effective mass (solid-state physics) 、 Band gap 、 Chemistry 、 Computational chemistry 、 Diethylenetriamine 、 Density functional theory 、 Ethylenediamine 、 Crystallography 、 Electronic band structure 、 Powder diffraction
摘要: The reaction of Hg(OAc)(2) with 1,4-benzenedithiol in ethylenediamine at 80 °C yields [Hg(SC(6)H(4)S)(en)](n), while the Pb(OAc)(2) diethylenetriamine 130 [Pb(SC(6)H(4)S)(dien)](n). Both products are crystalline materials, and structure determination by synchrotron X-ray powder diffraction revealed that both essentially one-dimensional metal-organic polymers -M-SC(6)H(4)S- repeat units. Diffuse reflectance UV-visible spectroscopy indicates band gaps 2.89 eV for [Hg(SC(6)H(4)S)(en)](n) 2.54 [Pb(SC(6)H(4)S)(dien)](n), density functional theory (DFT) calculations yielded 2.24 2.10 eV, respectively. two compounds infinite metal atoms linked 1,4-benzenedithiolate, prototypical molecule single-molecule conductivity studies, yet neither compound has significant electrical as a pressed pellet. In case [Pb(SC(6)H(4)S)(dien)](n) indicate fairly flat bands therefore low carrier mobilities, conduction does have moderate dispersion calculated electron effective mass 0.29·m(e). Hybridization empty Hg 6s orbital SC(6)H(4)S orbitals leads to dispersion, suggests similar hybrid materials smaller will be good semiconductors.
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sci-hub.se 参考文章(46)
Otfried Madelung, Semiconductors: Data Handbook ,(2003)
Kevin H. Stone, Dayna L. Turner, Mayank Pratap Singh, Thomas P. Vaid, Peter W. Stephens, Hidden Superlattice in Tl2(SC6H4S) and Tl2(SeC6H4Se) Solved from Powder X-ray Diffraction Acta Crystallographica Section B-structural Science. ,vol. 67, pp. 409- 415 ,(2011) , 10.1107/S0108768111030692
Huaxiang Fu, Jing Li, Density-functional study of organic–inorganic hybrid single crystal ZnSe(C2H8N2)1/2 The Journal of Chemical Physics. ,vol. 120, pp. 6721- 6725 ,(2004) , 10.1063/1.1665804
A. A. Coelho, Indexing of powder diffraction patterns by iterative use of singular value decomposition Journal of Applied Crystallography. ,vol. 36, pp. 86- 95 ,(2003) , 10.1107/S0021889802019878
Per-Anders Glans, Timothy Learmonth, Kevin E. Smith, Jinghua Guo, Aron Walsh, Graeme W. Watson, Fabio Terzi, Russell G. Egdell, Experimental and theoretical study of the electronic structure of HgO and Tl2O3 Physical Review B. ,vol. 71, pp. 235109- ,(2005) , 10.1103/PHYSREVB.71.235109
Qichun Zhang, Zhien Lin, Xianhui Bu, Tao Wu, Pingyun Feng, Solvothermal Conversion of Discrete Cubic Cadmium Thiolate Cluster into Supertetrahedral Cluster Decorating Quartz-Type Chiral Superlattice Chemistry of Materials. ,vol. 20, pp. 3239- 3241 ,(2008) , 10.1021/CM702874S
Xiaoying Huang, R Harry IV, IV Heulings, Vina Le, Jing Li, Inorganic−Organic Hybrid Composites Containing MQ (II−VI) Slabs: A New Class of Nanostructures with Strong Quantum Confinement and Periodic Arrangement Chemistry of Materials. ,vol. 13, pp. 3754- 3759 ,(2001) , 10.1021/CM010403D
Xiaoying Huang, Jing Li, Huaxiang Fu, The First Covalent Organic-Inorganic Networks of Hybrid Chalcogenides: Structures That May Lead to a New Type of Quantum Wells Journal of the American Chemical Society. ,vol. 122, pp. 8789- 8790 ,(2000) , 10.1021/JA002224N
A. D. Rae, D. C. Craig, I. G. Dance, M. L. Scudder, P. A. W. Dean, M. A. Kmetic, N. C. Payne, J. J. Vittal, The Pseudo-Symmetric Structure of Pb(SPh)2 Acta Crystallographica Section B-structural Science. ,vol. 53, pp. 457- 465 ,(1997) , 10.1107/S0108768196015819
Kim J Yaghi, OM, O'Keeffe, M, Ockwig NW, Chae, HK, Eddaoudi M, Reticular synthesis and the design of new materials Nature. ,vol. 423, pp. 705- 714 ,(2003) , 10.1038/NATURE01650