Phosphorescence and Structure of a Tetrameric Copper(I)-Amide Cluster
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- 作者：Alicia M. James ; Ravi K. Laxman ; Frank R. Fronczek ; and Andrew W. Maverick
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：July 27, 1998
- 年：1998
- 卷：37
- 期：15
- 页码：3785 - 3791
- 全文大小：108K
- 年卷期：v.37,no.15(July 27, 1998)
- ISSN：1520-510X
文摘
The colorless copper(I) cluster [CuN(Si(CH3)3)2]4, which contains a square-planar Cu4N4 core, phosphoresces inCH2Cl2 solution (
max, 512 nm; lifetime, 30 
s) and in the solid state at room temperature. Its electronic absorptionspectrum in CH2Cl2 consists of two intense bands at 283 and 246 nm; these transitions, as well as thephosphorescence, are likely to involve population of MOs reflecting substantial Cu···Cu interactions. Solid [CuN(Si(CH3)3)2]4 luminesces with approximately the same spectrum as that of the CH2Cl2 solutions. At 77 K, thesolid-state luminescence red-shifts slightly (max, 524 nm) and narrows substantially (fwhm, 2400 cm-1; vs 3500cm-1 at 300 K); the emission lifetime in glassy Et2O solution is 690 s. X-ray analysis of crystals of [CuN(Si(CH3)3)2]4 at 130 and 296 K shows that, although the previously reported structure solution (in space group I2/m,with the molecules on 2/m sites; Eur. J. Solid State Inorg. Chem. 1992, 29, 573-583) is approximately correct,the lattice is actually primitive, P2/n, and the only crystallographically required symmetry element for the moleculeis a 2-fold axis. C24H72Cu4N4Si8: monoclinic, space group P2/n, Z = 2. At 130 K, a = 9.285(3) Å, b = 13.393(3) Å, c = 17.752(5) Å, and 
= 90.53(2)
. [At 296 K, a = 9.3773(4) Å, b = 13.5836(7) Å, c = 17.814(2) Å,and = 90.207(7).] At 130 K, the Cu and N atoms in the cluster are planar within 0.007 Å, and the Cu-N andCu···Cu distances are 1.917(4)-1.925(4) and 2.6770(7)-2.6937(7) Å, respectively. Despite the low volatilityof the compound, it can be used as a precursor for chemical vapor deposition (CVD) of copper metal, under H2carrier gas, with both source and substrate at ca. 200 C. Smaller amounts of Cu metal films are also depositedwhen the substrate temperature is as low as 145 C (in the dark) or 136-138 C (under Pyrex-filtered Xe arclamp illumination). Thus, Cu CVD with this precursor shows slight photochemical enhancement.
max, 512 nm; lifetime, 30 s) and in the solid state at room temperature. Its electronic absorptionspectrum in CH2Cl2 consists of two intense bands at 283 and 246 nm; these transitions, as well as thephosphorescence, are likely to involve population of MOs reflecting substantial Cu···Cu interactions. Solid [CuN(Si(CH3)3)2]4 luminesces with approximately the same spectrum as that of the CH2Cl2 solutions. At 77 K, thesolid-state luminescence red-shifts slightly (max, 524 nm) and narrows substantially (fwhm, 2400 cm-1; vs 3500cm-1 at 300 K); the emission lifetime in glassy Et2O solution is 690 s. X-ray analysis of crystals of [CuN(Si(CH3)3)2]4 at 130 and 296 K shows that, although the previously reported structure solution (in space group I2/m,with the molecules on 2/m sites; Eur. J. Solid State Inorg. Chem. 1992, 29, 573-583) is approximately correct,the lattice is actually primitive, P2/n, and the only crystallographically required symmetry element for the moleculeis a 2-fold axis. C24H72Cu4N4Si8: monoclinic, space group P2/n, Z = 2. At 130 K, a = 9.285(3) Å, b = 13.393(3) Å, c = 17.752(5) Å, and = 90.53(2). [At 296 K, a = 9.3773(4) Å, b = 13.5836(7) Å, c = 17.814(2) Å,and = 90.207(7).] At 130 K, the Cu and N atoms in the cluster are planar within 0.007 Å, and the Cu-N andCu···Cu distances are 1.917(4)-1.925(4) and 2.6770(7)-2.6937(7) Å, respectively. Despite the low volatilityof the compound, it can be used as a precursor for chemical vapor deposition (CVD) of copper metal, under H2carrier gas, with both source and substrate at ca. 200 C. Smaller amounts of Cu metal films are also depositedwhen the substrate temperature is as low as 145 C (in the dark) or 136-138 C (under Pyrex-filtered Xe arclamp illumination). Thus, Cu CVD with this precursor shows slight photochemical enhancement.