A Solid-State Spectral Effect in Eclipsed Tetracyanonickelates: X-ray Crystal Structure, Polarized Specular Reflectance Spectroscopy, and ZINDO Modeling of Sr[Ni(CN)4]·5H2O,
详细信息 查看全文
- 作者：Frank R. Fronczek ; Terry J. Delord ; Steven F. Watkins ; Petia Gueorguieva ; George G. Stanley ; Annegret S. Zizza ; Jeffrey B. Cornelius ; Yves A. Mantz ; and Ronald L. Musselman
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：November 3, 2003
- 年：2003
- 卷：42
- 期：22
- 页码：7026 - 7036
- 全文大小：764K
- 年卷期：v.42,no.22(November 3, 2003)
- ISSN：1520-510X
文摘
Crystal structures of three Ni(CN)42- salts all with eclipsed ligands and varying axial stacking arrangements arepresented. The absorption spectra of all three salts show a slight red shift in the x,y-polarizations and a large redshift in their z-polarizations upon crystallization from solution. Semiempirical ZINDO calculations provide a goodmodel of the solid state, even with only a three-molecule segment, allowing reproduction of the red-shifting andintensity increase upon crystallization found experimentally. The modified nickel 
hars/beta2.gif" BORDER=0 ALIGN="middle">s,p bonding parameter of -5found appropriate for Ni coordination in our previous studies of single Ni(CN)42- planes and a helically stackedCs2[Ni(CN)4]·H2O crystal was changed to -3 for the more parallel-stacked Ni(CN)42- planes in this case, while hars/beta2.gif" BORDER=0 ALIGN="middle">dwas retained at -41. Crystal data are as follows: Na2[Ni(CN)4]·3H2O, triclinic space group P
, a = 7.2980(10) Å,b = 8.8620(10) Å, c = 15.132(2) Å, hars/alpha.gif" BORDER=0> = 89.311(5)
, hars/beta2.gif" BORDER=0 ALIGN="middle"> = 87.326(5), hars/gamma.gif" BORDER=0 > = 83.772(6), V = 971.8(2) Å3, T = 100K, Z = 4, R = 0.024, Rw = 0.064; Sr[Ni(CN)4]·5H2O, monoclinic space group C2/m, a = 10.356(2) Å, b =15.272(3) Å, c = 7.1331(10) Å, hars/beta2.gif" BORDER=0 ALIGN="middle"> = 98.548(12), V = 1115.6(3) Å3, T = 100 K, Z = 4, R = 0.024, Rw = 0.059;Rb2[Ni(CN)4]·1.05H2O, triclinic space group P, a = 8.6020(10) Å, b = 9.6930(10) Å, c = 12.006(2) Å, hars/alpha.gif" BORDER=0> =92.621(6), hars/beta2.gif" BORDER=0 ALIGN="middle"> = 94.263(6), hars/gamma.gif" BORDER=0 > = 111.795(10), V = 924.0(2) Å3, T = 100 K, Z = 4, R = 0.034, Rw = 0.067.
hars/beta2.gif" BORDER=0 ALIGN="middle">s,p bonding parameter of -5found appropriate for Ni coordination in our previous studies of single Ni(CN)42- planes and a helically stackedCs2[Ni(CN)4]·H2O crystal was changed to -3 for the more parallel-stacked Ni(CN)42- planes in this case, while hars/beta2.gif" BORDER=0 ALIGN="middle">dwas retained at -41. Crystal data are as follows: Na2[Ni(CN)4]·3H2O, triclinic space group P, a = 7.2980(10) Å,b = 8.8620(10) Å, c = 15.132(2) Å, hars/alpha.gif" BORDER=0> = 89.311(5), hars/beta2.gif" BORDER=0 ALIGN="middle"> = 87.326(5), hars/gamma.gif" BORDER=0 > = 83.772(6), V = 971.8(2) Å3, T = 100K, Z = 4, R = 0.024, Rw = 0.064; Sr[Ni(CN)4]·5H2O, monoclinic space group C2/m, a = 10.356(2) Å, b =15.272(3) Å, c = 7.1331(10) Å, hars/beta2.gif" BORDER=0 ALIGN="middle"> = 98.548(12), V = 1115.6(3) Å3, T = 100 K, Z = 4, R = 0.024, Rw = 0.059;Rb2[Ni(CN)4]·1.05H2O, triclinic space group P, a = 8.6020(10) Å, b = 9.6930(10) Å, c = 12.006(2) Å, hars/alpha.gif" BORDER=0> =92.621(6), hars/beta2.gif" BORDER=0 ALIGN="middle"> = 94.263(6), hars/gamma.gif" BORDER=0 > = 111.795(10), V = 924.0(2) Å3, T = 100 K, Z = 4, R = 0.034, Rw = 0.067.