2,8,15,18,21,24,31,37,44,47,50,53-Dodeca-oxahepta-cyclo-[52.4.0.0(4,35).0(6,33).0(9,14).0(25,30).0(38,43)]octa-penta-conta-1(54),4,6(33),9(14),10,12,25(30),26,28,34,38(43),39,41,55,57-penta-deca-ene di-chloro-methane disolvate.

In the title compound, C46H50O12·2CH2Cl2, each dual 20-crown-6 unit crystallizes with two di-chloro-methane solvent mol-ecules. The crown unit mol-ecule lies about an inversion centre located at the central benzene ring. The two crown ring groups adopt an anti conformation, stabilized by weak intra-molecular C-H⋯O inter-actions.

9-[3-(Carbazol-9-yl)-5-methyl-phen-yl]carbazole.

The title compound, C31H22N2, crystallizes with two symmetry-independent mol-ecules in the asymmetric unit. The mol-ecules have slightly different conformations, the dihedral angles between the central phenyl ring and the carbazolyl groups being 56.29 (4) and 59.

2,9,12,15,18,25,27,34,37,40,43,50-Dodeca-oxa-56-aza-hepta-cyclo-[24.24.5.1(51,55).0(3,8).0(19,24).0(28,33).0(44,49)]hexa-penta-conta-3,5,7,19(24),20,22,28(33),29,31,44,46,48,51,53,55-penta-deca-ene.

The title compound, C(43)H(45)NO(12), was prepared from the reaction of 2,6-bis-(dibromo-meth-yl)pyridine and bis-phenol in the presence of caesium carbonate as a base. The central ring makes dihedral angles of 64.83 (6), 13.

6,7-Bis(bromo-meth-yl)-2,11,18,21,24,27-hexa-oxatetra-cyclo-[26.4.0.0.0]dotriaconta-1(28),4,6,8,12(17),13,15,29,31-nona-ene dichloro-methane monosolvate.

The title 20-crown-6 unit, C(28)H(30)Br(2)O(6)·CH(2)Cl(2), consisting of three benzo groups and triethyl-ene glycol was prepared from the reaction of 1,2,4,5-tetra-kis-(bromo-meth-yl)benzene and bis-phenol in the presence of sodium hydride. In the crystal, one O atom of the central ethyl-ene glycol in the triethyl-ene glycol unit exhibits an exo conformation as a result of intra-molecular C-H⋯O hydrogen bonds. The crown unit and the solvent mol-ecule are linked by weak C-H⋯O hydrogen bonds.

Unsymmetrical calixcrowns incorporating hard and soft loops as a new scaffold for multinuclear endo/exocyclic complexation and networking.

Unsymmerical calix[4]crowns containing [(O(4)S)(O(5))] (L(1)) and [(O(4)S(2))(O(5))] (L(2)) as crown loops were employed as new scaffolds both for complexation studies and for network formation. Reactions of L(1) and L(2) with KI in the presence of CuI afforded a copper(I) iodide cluster linked 1D-type endocyclic dipotassium(I) complex [K(2)(L(1))(Cu(7)I(9))](n) (1) and a copper(I) iodide cluster linked 1D-type endocyclic monopotassium(I) complex [KL(2)(mu(2)-Cu(3)I(4))](n) (2), respectively. By comparison, the reaction of L(2) with KPF(6) in the presence of CuI and HgI(2) afforded the 1-D endocyclic potassium(I) complex [K(L(2))(CuHgI(4))](n) (3), linked with a CuHgI(4) cluster unit.

2,9,16,19,22,25-Hexaoxatetra-cyclo-[24.4.0.2.0]dotriaconta-1(26),4,6,10(15),11,13,27,29,31-nona-ene.

The title 22-crown-6 unit, C(26)H(28)O(6), comprising of three benzo groups and triethyl-ene glycol, was prepared by the reaction of α,α'-dibromo-p-xylene with 1,8-bis-(2-hydroxy-phen-oxy)-3,6-dioxaoctane in the presence of Cs(2)CO(3) with tetra-hydro-furan (THF) and recrystallized from dichloro-methane-hexane (1:20 v/v) at room temperature. In the mol-ecular structure, two O atoms of the central ethyl-ene glycol in the triethyl-ene glycol unit exhibit exo conformations due to intra-molecular C-H⋯O inter-actions. A number of C-H⋯O and C-H⋯π inter-molecular inter-actions contribute to the stabilization of the crystal packing.

Networking of calixcrowns: from heteronuclear endo/exocyclic coordination polymers to a photoluminescence switch.

Solvato-PL switching and shrinking-and-opening process: we present two CuI coordination polymers of calix[4]-bis-monothiacrown (L) obtained in the absence (1) and presence (2) of KI. The structures show not only very unusual CuI-based network arrangements but also unique reversible photolunimescence switching behavior induced by removal of coordinated solvent. Furthermore, upon inclusion of K+ ions the crown ring shrinks leading to "opening" of opposite aromatic rings in the host calixarene unit, rare behavior for this class of compound.

Temperature-dependent 3-D CuI coordination polymers of calix[4]-bis-dithiacrown: crystal-to-crystal transformation and photoluminescence change on coordinated solvent removal.

The temperature-dependent assembly of two 3-D CuI coordination polymers containing calix[4]-bis-thiacrown with different networking motifs are reported. Upon removal of the coordinated solvent molecules the initial solvent-coordinated polymer undergoes a unique single-crystal-to-single-crystal transformation to the desolvated polymer. Structural characteristics observed in the solvent-coordinated and the desolvated polymers also reveal related solvato-photolunimescence "off-on" behavior.

Calix[4]bis(thiacrown): assembly of an endocyclic disilver(I) complex and exocyclic 3D copper(I) coordination polymers.

Calix[4]bis(thiacrown-5) (L) with 1,3-alternating conformation was employed as a strong dinucleating ligand for the soft metal ions AgI and CuI. The reaction of L with AgPF6 afforded a discrete endo-coordinated disilver(I) complex 1, [Ag2L](PF6)2. In contrast, mixed products (2a + 2b) consisting of 3D networks were obtained from the reaction of L and CuI; 2b linked with a Cu4I4 cubane unit was shown to generate photoluminescence, while 2a linked with a Cu2I2 rhomboid unit does not.

Calix[4]thiacrowns as ditopic hosts for homo- and heterobinuclear accommodation: first report of a chopsticks-type pi-coordination.

[reaction: see text] Calix[4]thiacrowns with hetero-L(1) and a homodonor set (L(2)) were synthesized and characterized by X-ray analysis. From the reaction of L(2) with AgPF(6), disilver complex [Ag(2)(L(2))](PF(6))(2) (1) was isolated. By comparing 1,3-alternate conformations of L(2) and 1, we found a considerable decrease of dihedral angles of two opposite aromatic rings upon complexation.

Silver ion shuttling in the trimer-mimic thiacalix[4]crown tube.

Novel 1,3-alternate calix-thiacalix[4]crown trimers bearing crown-5 and crown-6 were prepared. As proven by X-ray diffraction, in a 1:2 mole ratio of ligand to metal ion, the Cs(+) and K(+) ions prefer to be encapsulated in the trimeric thiacalix[4]crown-6 and crown-5, respectively. On the contrary, the Ag(+) ion was found to be entrapped in the central thiacalix spacer as a 1:1 complex confirmed by (1)H NMR spectrosocpy.