Channel forming organic crystals: guest alignment and properties

Abstract

Purely organic solid state materials providing nanometre sized parallel channels are suited for physical property design. In this tutorial review, key materials in this field are reviewed along with new directions forming porous covalent and polymeric networks. Among many known host materials, perhydrotriphenylene (PHTP), tris-(o-phenylenedioxy)-cyclotriphosphazene (TPP) and members of the 2,4,6-tris-(4-halo-phenoxy)-1,3,5 triazine (4-X-POT) family are prime materials for hosting guest molecules featuring diverse physical functionality.

ESR study of the molecular orientation and dynamics of stable organic radicals included in the 1‐D organic nanochannels of 2,4,6‐tris‐4‐(chlorophenoxy)‐1,3,5‐triazine

“…As templates to align the functional materials in a 1‐D manner, not only porous coordination polymers (PCPs) having various pore size, shape or porous surface states are good candidates but also porous organic materials . In particular, the latter is available as templates to construct new 1‐D functional ‘organic’ materials.…”

Porous Organic Molecular Frameworks with Extrinsic Porosity: A Platform for Carbon Storage and Separation

“…More interestingly, the desolvated HOF‐8 a demonstrates permanent porosity with highly selective adsorption of CO 2 over N 2 /H 2 (Figure ), as well as adsorption of C 6 H 6 over other hydrocarbons (i.e., n ‐hexane, cyclohexane, toluene, or pxylene) at ambient temperature. Of special note, the adsorption of CO 2 for HOF‐8 a at 298 K and 1 atm (57.3 cm 3 (STP)⋅g −1 ) is higher than that of any other crystalline porous organic materials reported in the literature …”

Redox-promoted associative assembly of metal–organic materials

“…Milling in the presence of a 1 : 1 mixture of PhMe and H 2 O affords the trinuclear complex 11 , composed of three pentacoordinate Zn( SQ ) 2 units surrounding a central TPVB ligand. (§ §Crystallographic data: compound 3 : Zn 2 SQ 4 Py 2 , (CCDC ), orthorhombic, Pbca , a = 10.8810(16) Å, b = 19.5543(28) Å, c = 29.4419(42) Å, Z = 4, R 1 = 0.083, w R 2 = 0.136 (for 4206 reflections with I ≥ 2 σ I ), R 1 = 0.177, w R 2 = 0.163 (for all reflections), S = 1.056; compound 4 : Zn SQ 2 Py 2 , (CCDC ), monoclinic, P 2 1 / c , a = 10.671(5) Å; b = 19.665(9) Å; c = 17.723(8) Å; β = 97.137(7)°; Z = 4, R 1 = 0.108, w R 2 = 0.137 (for 3107 reflections with I ≥ 2 σ I ), R 1 = 0.108, w R 2 = 0.193 (for all reflections), S = 1.015; compound 5 : Zn SQ 2 NMI , (CCDC ), orthorhombic, Pbca , a = 12.2437(8) Å, b = 18.3841(11) Å, c = 30.3846(19) Å, Z = 8, R 1 = 0.049, w R 2 = 0.093 (for 3668 reflections with I ≥ 2 σ I ), R 1 = 0.120, w R 2 = 0.126 (for all reflections), S = 0.992; compound 6 : Zn SQ 2 NMI 2 , (CCDC ), monoclinic, P 2 1 , a = 10.6541(9) Å, b = 19.7432(17) Å, c = 17.8899(15) Å, β = 99.193(1)°, Z = 4, R 1 = 0.058, w R 2 = 0.137 (for 4265 reflections with I ≥ 2 σ I ), R 1 = 0.108, w R 2 = 0.163 (for all reflections), S = 1.016; compound 7 : Zn SQ 2 Phen , (CCDC ) monoclinic, P 2 1 / c , a = 10.404(3) Å, b = 32.256(8) Å, c = 13.672(3) Å, β = 111.664(4)°, Z = 4, R 1 = 0.081, w R 2 = 0.175 (for 2973 reflections with I ≥ 2 σ I ), R 1 = 0.289, w R 2 = 0.297 (for all reflections), S = 1.066; compound 9 : [Zn( SQ ) 2 ] 2 ( BVPB ), (CCDC ), monoclinic, P 21/ n , a = 12.6164(1) Å, b = 18.4537(2) Å, c = 15.3934(2) Å, β = 103.538(1)°, Z = 4, R 1 = 0.0334, w R 2 = 0.1042 (for 5329 reflections with I ≥ 2 σ I ), R 1 = 0.0428, w R 2 = 0.1152 (for all reflections), S = 0.854; compound 10 : [Zn( SQ ) 2 ]( BVPB )·toluene, (CCDC ), monoclinic, P 2 1 / n , a = 7.6947(9) Å, b = 13.1945(15) Å, c = 27.271(3) Å, β = 95.507(2)°, Z = 2, R 1 = 0.058, w R 2 = 0.117 (for 3753 reflections with I ≥ 2 σ I ), R 1 = 0.132, w R 2 = 0.143 (for all reflections), S = 1.001; compound 11 : [Zn( SQ ) 2 ] 3 ( TVPB )·toluene solvate, (CCDC ) triclinic, P 1, a = 15.4724(16) Å, b = 15.4781(16) Å, c = 28.908(3) Å, α = 78.730(4)°, β = 88.358(4)°, γ = 60.122(3)°, Z = 2, R 1 = 0.1496, w R 2 = 0.3209 (for 15 246 reflections with I ≥ 2 σ I ), R 1 = 0.1811, w R 2 = 0.3344 (for all reflections), S = 1.216.) Crystal structure analysis reveals that the trigonal complexes arrange into a loosely packed structure 74–76 with highly disordered solvent molecules occupying otherwise vacant cavities. According to thermogravimetric analysis, the included solvent is removed by heating at 50 °C under reduced pressure.…”