ABSTRACT
The isolation and characterization of small sulfur allotropes have long remained unachievable because of their extreme lability. This study reports the first direct observation of disulfur (S2) with X-ray crystallography. Sulfur gas was kinetically trapped and frozen into the pores of two Cu-based porous coordination networks containing interactive iodide sites. Stabilization of S2 was achieved either through physisorption or chemisorption on iodide anions. One of the networks displayed shape selectivity for linear molecules only, therefore S2 was trapped and remained stable within the material at room temperature and higher. In the second network, however, the S2 molecules reacted further to produce bent-S3 species as the temperature was increased. Following the thermal evolution of the S2 species in this network using X-ray diffraction and Raman spectroscopy unveiled the generation of a new reaction intermediate never observed before, the cyclo-tri-sulfur dication (cyclo-S3 (2+)). It is envisaged that kinetic guest trapping in interactive crystalline porous networks will be a promising method to investigate transient chemical species.
ABSTRACT
A net gain: A kinetically assembled, but thermally stable network is obtained using the labile metal species [Cu4 I4 (PPh3 )4 ]. The network uniquely adsorbs I2 by chemisorption through I3 (-) formation. The chemisorbed I2 readily desorbs above 380â K owing to the dynamic motion of the framework. A thermodynamically assembled network physisorbs I2 , which is an exact fit for the channel.
ABSTRACT
Multitemperature X-ray structure analyses and photoemission spectra of [Cu(4)I(4)(PPh(3))(4)] in two polymorphic crystals reveal that the cubane-like framework is flexibly distorted effecting luminescence thermochromism.
