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.
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 380 K owing to the dynamic motion of the framework. A thermodynamically assembled network physisorbs I2 , which is an exact fit for the channel.
Im Netz gefangen: Ein kinetisch angeordnetes, aber thermisch stabiles Netzwerk wird unter Verwendung der labilen Metallspezies [Cu4I4(PPh3)4] erhalten. In einzigartiger Weise adsorbiert es I2 durch Chemisorption über I3−‐Bildung. Das chemisorbierte I2 desorbiert leicht bei >380 K wegen der dynamischen Bewegung des Gerüstes. Ein thermodynamisch angeordnetes Netzwerk physisorbiert I2, das exakt in den Kanal passt.
Reported here are the isolation and direct observation of extremely reactive S2 and its conversion into bent-S3
via a cyclo-S3
2+ intermediate on interactive sites in porous coordination networks.
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