New Host Polymeric Framework and Related Polar Guest Cocrystals Paola Rizzo, Christophe Daniel, Anna De Girolamo Del Mauro, and Gaetano Guerra* Dipartimento di Chimica, UniVersita ` degli Studi di Salerno, Via Ponte Don Melillo, 84084 Fisciano (SA), Italy ReceiVed April 24, 2007 ReVised Manuscript ReceiVed June 21, 2007 Nanoporous crystalline structures can be achieved for a large variety of chemical compounds: inorganic (e.g., zeolites), 1 metal-organic, 2 as well as organic. 3 These materi- als, often referred as inorganic, metal-organic, and organic “frameworks”, are relevant for molecular storage, recogni- tion, and separation techniques. Recently, a “polymeric framework”, i.e., a semicrystalline polymeric material presenting a nanoporous crystalline phase, has also been discovered. 4-6 In fact, the δ-phase of syndio- tactic polystyrene (s-PS) presents two identical cavities and eight styrene monomeric units per unit cell 4 and is promising for applications in chemical separations and air/water purification 5 as well as sensorics. 6 The δ-phase rapidly and selectively absorbs low-molec- ular-mass guest molecules even at very low activities, producing clathrate 7 and intercalate 8 cocrystals (also referred to as molecular-complex crystalline phases). The self- assembling of this polymeric framework and several active guest molecules into cocrystals can be relevant for several applications. In fact, polymer-based host-guest cocrystals not only reduce guest diffusivity and prevent guest self- aggregation (without recurring to chemical reactions), but also allow control of the location and orientation of active guest molecules, by controlling the orientation (axial 9 or planar 10 ) of the host crystalline phase. On this basis, films presenting s-PS/active-guest cocrystals have been proposed as advanced materials, mainly for optical applications (e.g., fluorescent, photoreactive, and chromophore materials). 11 Very recently, it has been shown that the δ-phase, although apolar, is also able to absorb, from solutions in suitable carrier-solvents, high-polarity guests, eventually leading to highly stable apolar-host/polar-guest clathrate phases. 12 Ac- cording to that study, the formation of these cocrystals from δ-form s-PS occurs only for polar-guest molecules having a volume lower than the limiting maximum value (0.25-0.26 nm 3 ) observed for s-PS clathrate phases. 8b In particular, the bulkiest observed guest was trans-4-methoxy--nitro-styrene, which presents a hyperpolarizability  ) 17 × 10 30 esu. 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