Exposure of the polymeric solid [CuI(4-pic)](infinity) (pic = picoline = methyl pyridine) to liquid or vapor toluene leads to disappearance of its room-temperature blue emission (lambda (max) 437 nm) and the appearance of a yellow emission (lambda (max) 580 nm) characteristic of the [CuI(4-pic)](4) tetramer. The process is reversed when the latter is exposed to liquid or vapor n-pentane. Analogous transformations between the tetrameric and polymeric forms do not occur when the 3-picoline analogues [CuI(3-pic)](x) are similarly treated. Single-crystal X-ray diffraction studies on the compounds [CuIL](infinity) and [CuIL](4) (L = 3-, 4-pic) indicate that the 4-pic tetranuclear isomer incorporates toluene into its solid phase to give a material with the composition [CuI(4-pic)](4). 2C(6)H(5)CH(3), but the other three phases are solvent-free. The chains in the two polymeric phases exhibit double-zigzag configurations, also commonly observed in zeolitic tetrahedral structures. In both polymeric phases, the chains propagate along the monoclinic b axis. The 3-pic tetrameric phase can be described as a close-packed structure of [CuIL](4) units, whereas tetramers in the 4-pic phase form infinite columns along the unique tetragonal c axis segregated by four columns of toluene pairs. These structural differences explain the different behaviors during the phase transformation between tetrameric and polymeric polymorphs of the 3-pic and 4-pic compounds.

Solvent- and vapor-induced isomerization between the luminescent solids [CuI(4-pic)](4) and [CuI(4-pic)](infinity) (pic = methylpyridine). The structural basis for the observed luminescence vapochromism / E. Cariati, X. Bu, P.C. Ford. - In: CHEMISTRY OF MATERIALS. - ISSN 0897-4756. - 12:11(2000), pp. 3385-3391.

Solvent- and vapor-induced isomerization between the luminescent solids [CuI(4-pic)](4) and [CuI(4-pic)](infinity) (pic = methylpyridine). The structural basis for the observed luminescence vapochromism

E. Cariati
Primo
;
2000

Abstract

Exposure of the polymeric solid [CuI(4-pic)](infinity) (pic = picoline = methyl pyridine) to liquid or vapor toluene leads to disappearance of its room-temperature blue emission (lambda (max) 437 nm) and the appearance of a yellow emission (lambda (max) 580 nm) characteristic of the [CuI(4-pic)](4) tetramer. The process is reversed when the latter is exposed to liquid or vapor n-pentane. Analogous transformations between the tetrameric and polymeric forms do not occur when the 3-picoline analogues [CuI(3-pic)](x) are similarly treated. Single-crystal X-ray diffraction studies on the compounds [CuIL](infinity) and [CuIL](4) (L = 3-, 4-pic) indicate that the 4-pic tetranuclear isomer incorporates toluene into its solid phase to give a material with the composition [CuI(4-pic)](4). 2C(6)H(5)CH(3), but the other three phases are solvent-free. The chains in the two polymeric phases exhibit double-zigzag configurations, also commonly observed in zeolitic tetrahedral structures. In both polymeric phases, the chains propagate along the monoclinic b axis. The 3-pic tetrameric phase can be described as a close-packed structure of [CuIL](4) units, whereas tetramers in the 4-pic phase form infinite columns along the unique tetragonal c axis segregated by four columns of toluene pairs. These structural differences explain the different behaviors during the phase transformation between tetrameric and polymeric polymorphs of the 3-pic and 4-pic compounds.
Settore CHIM/03 - Chimica Generale e Inorganica
2000
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/209461
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