A Detailed Study of the Vapochromic Behavior of {Tl[Au(C6Cl5)2]}n
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- 作者：Eduardo J. Ferná ; ndez ; José ; M. Ló ; pez-de-Luzuriaga ; Miguel Monge ; Manuel Montiel ; M. Elena Olmos ; Javier Pé ; rez ; Antonio Laguna ; Fernando Mendizabal ; Ahmed A. Mohamed ; and Joh
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：June 14, 2004
- 年：2004
- 卷：43
- 期：12
- 页码：3573 - 3581
- 全文大小：471K
- 年卷期：v.43,no.12(June 14, 2004)
- ISSN：1520-510X
文摘
The linear-chain polymer {Tl[Au(C6Cl5)2]}n, 1, reacts in the solid state and in solution with different volatile organiccompounds such as tetrahydrofuran, acetone, tetrahydrothiophene, 2-fluoropyridine, acetonitrile, acetylacetone, andpyridine. Solid-state exposure of 1 to vapors of the above VOCs produces a selective and reversible change in itscolor that is perceptible to the human eye and even deeper under UV irradiation, allowing 1 to function as a sensorfor these VOCs. Heating the samples exposed to the VOCs for a few minutes at 100
C regenerates the originalmaterial without degradation, even after several exposure/heating cycles. The reversibility is further confirmed byX-ray powder diffraction measurements of complex 1 before and after exposure to vapors and again after heating thesamples. The products obtained by reactions of complex 1 with the above VOCs as ligands in solution containextended linear chains of alternating gold and thallium centers with two molecules of the organic ligands attached toeach thallium atom. The stoichiometry of these materials has been confirmed by single-crystal X-ray diffraction as{Tl(THF)2[Au(C6Cl5)2]}n, 3, and {Tl(acacH)2[Au(C6Cl5)2]}n, 5. Comparison of FT-IR, UV-vis, and luminescence spectraat room temperature and at 77 K of the solid samples of complexes 2-9 with the spectra of complex 1 after itsexposure to VOCs suggests interaction occurs between the organic VOCs and thallium in each case. Thermogravimetricanalyses data indicate that all the thallium centers in these derivatives of complex 1 are neither fully nor equallycoordinatively saturated. The materials formed appear to be intermediates between complex 1 with no VOCs attachedand complexes 3-9 which contain two organic ligands coordinated to each thallium. A crystal structure analyses ofone of these intermediates, {Tl(THF)0.5[Au(C6Cl5)2]}n, 1·0.5THF, confirms this. Density functional calculations are inaccord with the observed experimental results. Analysis reveals a substantial participation of the metal atoms intransitions that give rise to the observed emissions. Crystallographic data are as follows. For 1·0.5THF: triclinic, P
,a = 8.9296(1) Å, b = 11.2457(1) Å, c = 21.2465(3) Å, 
= 96.7187(7), 
= 92.5886(6), 
= 98.5911(8), V =2090.87(4) Å3, and Z = 2. For 3: monoclinic, P21/c, a = 26.4163(6) Å, b = 12.1619(2) Å, c = 28.0813(6) Å, =90, = 161.9823(6), = 90, V = 2790.51(10) Å3, and Z = 4. For 5: monoclinic, P21/c, a = 9.8654(2) Å, b =29.8570(5) Å, c = 11.6067(2) Å, = 90, = 114.5931(6), = 90, V = 3108.64(10) Å3, and Z = 4.
C regenerates the originalmaterial without degradation, even after several exposure/heating cycles. The reversibility is further confirmed byX-ray powder diffraction measurements of complex 1 before and after exposure to vapors and again after heating thesamples. The products obtained by reactions of complex 1 with the above VOCs as ligands in solution containextended linear chains of alternating gold and thallium centers with two molecules of the organic ligands attached toeach thallium atom. The stoichiometry of these materials has been confirmed by single-crystal X-ray diffraction as{Tl(THF)2[Au(C6Cl5)2]}n, 3, and {Tl(acacH)2[Au(C6Cl5)2]}n, 5. Comparison of FT-IR, UV-vis, and luminescence spectraat room temperature and at 77 K of the solid samples of complexes 2-9 with the spectra of complex 1 after itsexposure to VOCs suggests interaction occurs between the organic VOCs and thallium in each case. Thermogravimetricanalyses data indicate that all the thallium centers in these derivatives of complex 1 are neither fully nor equallycoordinatively saturated. The materials formed appear to be intermediates between complex 1 with no VOCs attachedand complexes 3-9 which contain two organic ligands coordinated to each thallium. A crystal structure analyses ofone of these intermediates, {Tl(THF)0.5[Au(C6Cl5)2]}n, 1·0.5THF, confirms this. Density functional calculations are inaccord with the observed experimental results. Analysis reveals a substantial participation of the metal atoms intransitions that give rise to the observed emissions. Crystallographic data are as follows. For 1·0.5THF: triclinic, P,a = 8.9296(1) Å, b = 11.2457(1) Å, c = 21.2465(3) Å, = 96.7187(7), = 92.5886(6), = 98.5911(8), V =2090.87(4) Å3, and Z = 2. For 3: monoclinic, P21/c, a = 26.4163(6) Å, b = 12.1619(2) Å, c = 28.0813(6) Å, =90, = 161.9823(6), = 90, V = 2790.51(10) Å3, and Z = 4. For 5: monoclinic, P21/c, a = 9.8654(2) Å, b =29.8570(5) Å, c = 11.6067(2) Å, = 90, = 114.5931(6), = 90, V = 3108.64(10) Å3, and Z = 4.