Orientational Control of Guest Molecules in an Organic Intercalation System by Host Polymer Tacticity

Abstract

Four kinds of stereoregular poly(muconic acid)s, which are synthesized by topochemical polymerization and subsequent solid-state hydrolysis, are used as the organic host materials for intercalation. We describe the reaction behavior and layered structure of intercalation compounds using stereoregular poly(muconic acid)s and n-alkylamines as host and guest, respectively. The packing structure of the guest alkylamines was determined by X-ray diffractions as well as IR and Raman spectroscopies. We have found that the orientation of the guest molecules is controlled by the host polymer tacticity, depending on the structure of the two-dimensional hydrogen-bonding network formed in the polymer sheets of the crystals.

Solid‐State Hosts by the Template Polymerization of Columnar Liquid Crystals: Locked Supramolecular Architectures around Chiral 2‐Amino Alcohols

“…This observation strongly suggests that a "template effect" certainly works in this system. In the cases of guests possessing only a C2 substituent, the enantioselections observed were at an unsatisfactory level regardless of the bulkiness of the substituent, and yet the favorable enantiomers were of the same configuration at the C2-position as that of the template (Table 4, entries [4][5][6]. From these results, we can deduce that the stereochemistry at the C1-position is a determinant factor of the enantioselection, whereas the substituent at the C2-position is likely to bring little influence, as long as either the C1-or C2-position of a 2-amino alcohol was substituted with an alkyl/aryl group.…”

“…[5] When a polymerizable mesogen (matrix) and another component (template) noncovalently interact with each other to form a liquid-crystalline (LC) structure, cavities with a well-defined structure complementary to the template are expected to be created by the in situ cross-linking of the matrix. Although polymerization reactions do not necessarily proceed in constrained architectures, such as in crystals, [6] the dynamic nature of the LC materials would permit an efficient crosslinking to "freeze in" the desired structure. In addition, considering the noncovalent nature of the linkage between the matrix and the template, the cross-linked materials should be applicable as solid-state hosts by removing and/or exchanging the template moiety (Scheme 1).…”

Physical Chemistry of Intercalated System

“…More convenient approach is usage of single-component catalysts of olefins polymerization. In particular, this concerns the Pd [142] (where dppp ¼ 1.3 Bis(diphenylphosphino)propane, OTs -n-toluene sulfonate) which is intercalated in synthetic hectorite modified by tetra(decyl)ammonium cations and performs gas phase polymerization of ethylene at 295 K with formation of high molecular polyethylene (PE extracted with toluene, M n ¼ 159,000, M w ¼ 262,000). After 2-h absorption of ethylene a dramatic increase in the silicate/catalyst size was observed followed by its collapse: in the composite produced after 24 h of polymerization there are absolutely no diffraction peaks of the silicate.…”

Selective adenine/cytosine cations in one-dimensional coordination polymers of manganese (II) and copper (II) 2,3-pyridinedicarboxylates

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One-dimensional coordination polymer {[1H,9H-ade] 2 [MnL 2 ]•4H 2 O} n (1) and {[1H,3H-cyt] 2 [CuL 2 ]•6H 2 O} n (2) (ade = adenine, cyt = cytosine, L = dianion of 2,3-pyridinedicarboxylic acid) are selectively synthesized and variable-temperature magnetic susceptibility measurements revealed weak antiferromagnetic interactions within the chains of 1 and 2 (J = − 0.29 cm − 1 for 1 and J = −0.03 cm − 1 for 2, according to the − 2J ij S i S j HDvV Hamiltonian formalism).The organic cations sandwiched between layers of metal-organic frameworks (MOF) serve as adjustable components to tune structure and properties [1][2][3][4][5][6][7][8][9]. Layered solid comprising of organic, metal phosphonate or metal halide anions are widely used in the synthesis and design of inorganic-organic lamellar solids [10][11][12].

…”

“…The organic cations sandwiched between layers of metal-organic frameworks (MOF) serve as adjustable components to tune structure and properties [1][2][3][4][5][6][7][8][9]. Layered solid comprising of organic, metal phosphonate or metal halide anions are widely used in the synthesis and design of inorganic-organic lamellar solids [10][11][12].…”