Mapping Out the Diversity of Lanthanide(III) Coordination Complexes Involving p-Sulfonatocalix[4,6]arenes

2020 ◽  
Vol 73 (6) ◽  
pp. 570
Author(s):  
Irene Ling ◽  
Mohamed Makha ◽  
Alexandre N. Sobolev ◽  
Yatimah Alias ◽  
Colin L. Raston
Keyword(s):  
Aqueous Media ◽  
Coordination Complexes ◽  
Cone Conformation ◽  
Partial Cone ◽  
Lanthanide Series ◽  
Hydrogen Bonded

Structurally authenticated complexes of the cone-shaped p-sulfonatocalix[4]arene and conformationally flexible p-sulfonatocalix[6]arene devoid of co-ligands/ancillary molecules are limited. Early and late members of the lanthanide series as their trivalent ions, La3+, Er3+, and Yb3+, form complexes from aqueous media under these conditions. For La3+ and Er3+, distinct hydrophobic and hydrophilic bilayers are formed with p-sulfonatocalix[4]arene, whereas for Yb3+, two complexes form that deviate from the well-known bilayer arrangement of calixarenes. Replacing the calixarene with p-sulfonatocalix[6]arene results in a hydrogen-bonded network with alternating hydrophobic–hydrophilic layers associated with primary coordination of Yb3+, with the larger macrocyclic calixarene in a partial cone conformation.

Self-Recognizing π-π Stacking Interactions Designed for the Generation of Ultrastable Mesoporous Hydrogen-Bonded Organic Frameworks

2019 ◽  
Author(s):  
KAIKAI MA ◽  
Peng Li ◽  
John Xin ◽  
Yongwei Chen ◽  
Zhijie Chen ◽  
...  
Keyword(s):  
Pore Size ◽  
Fiber Composite ◽  
Aqueous Media ◽  
Stacking Interactions ◽  
Mustard Gas ◽  
X Ray Diffraction ◽  
X Ray ◽  
Expansion Strategy ◽  
Π Stacking ◽  
Hydrogen Bonded

Creating crystalline porous materials with large pores is typically challenging due to undesired interpen-etration, staggered stacking, or weakened framework stability. Here, we report a pore size expansion strategy by self-recognizing π-π stacking interactions in a series of two-dimensional (2D) hydrogen–bonded organic frameworks (HOFs), HOF-10x (x=0,1,2), self-assembled from pyrene-based tectons with systematic elongation of π-conjugated molecular arms. This strategy successfully avoids interpene-tration or staggered stacking and expands the pore size of HOF materials to access mesoporous HOF-102, which features a surface area of ~ 2,500 m2/g and the largest pore volume (1.3 cm3/g) to date among all reported HOFs. More importantly, HOF-102 shows significantly enhanced thermal and chemical stability as evidenced by powder x-ray diffraction and N2 isotherms after treatments in chal-lenging conditions. Such stability enables the adsorption of dyes and cytochrome c from aqueous media by HOF-102 and affords a processible HOF-102/fiber composite for the efficient photochemical detox-ification of a mustard gas simulant.

scholarly journals Construction of Two Stable Co(II)-Based Hydrogen-Bonded Organic Frameworks as a Luminescent Probe for Recognition of Fe3+ and Cr2O72− in H2O

Molecules ◽  
2021 ◽  
Vol 26 (19) ◽  
pp. 5955
Author(s):  
Qi-Ying Weng ◽  
Ya-Li Zhao ◽  
Jia-Ming Li ◽  
Miao Ouyang
Keyword(s):  
Detection Limit ◽  
Aqueous Media ◽  
Three Dimensional ◽  
Cobalt Atom ◽  
High Sensitivity ◽  
X Ray Diffraction ◽  
Chlorobenzoic Acid ◽  
X Ray ◽  
Highly Sensitive ◽  
Hydrogen Bonded

A pair of cobalt(II)-based hydrogen-bonded organic frameworks (HOFs), [Co(pca)2(bmimb)]n (1) and [Co2(pca)4(bimb)2] (2), where Hpca = p-chlorobenzoic acid, bmimb = 1,3-bis((2-methylimidazol-1-yl)methyl)benzene, and bimb = 1,4-bis(imidazol-1-ylmethyl)benzene were hydrothermally synthesized and characterized through infrared spectroscopy (IR), elemental and thermal analysis (EA), power X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD) analyses. X-ray diffraction structural analysis revealed that 1 has a one-dimensional (1D) infinite chain network through the deprotonated pca− monodentate chelation and with a μ2-bmimb bridge Co(II) atom, and 2 is a binuclear Co(II) complex construction with a pair of symmetry-related pca− and bimb ligands. For both 1 and 2, each cobalt atom has four coordinated twisted tetrahedral configurations with a N2O2 donor set. Then, 1 and 2 are further extended into three-dimensional (3D) or two-dimensional (2D) hydrogen-bonded organic frameworks through C–H···Cl interactions. Topologically, HOFs 1 and 2 can be simplified as a 4-connected qtz topology with a Schläfli symbol {64·82} and a 4-connected sql topology with a Schläfli symbol {44·62}, respectively. The fluorescent sensing application of 1 was investigated; 1 exhibits high sensitivity recognition for Fe3+ (Ksv: 10970 M−1 and detection limit: 19 μM) and Cr2O72− (Ksv: 12960 M−1 and detection limit: 20 μM). This work provides a feasible detection platform of HOFs for highly sensitive discrimination of Fe3+ and Cr2O72− in aqueous media.

Calixarene Phosphorylation: Cation Control of Reaction Pathways

1993 ◽  
Vol 46 (11) ◽  
pp. 1673 ◽  
Author(s):  
LT Byrne ◽  
JM Harrowfield ◽  
DCR Hockless ◽  
BJ Peachey ◽  
BW Skelton ◽  
...  
Keyword(s):  
Phase Transfer ◽  
Tetrabutylammonium Bromide ◽  
Crystal Structure Analysis ◽  
Bidentate Ligand ◽  
Tetraethylammonium Bromide ◽  
Cone Conformation ◽  
Formation Reaction ◽  
Partial Cone ◽  
Major Reaction Product ◽  
Major Reaction

The hydroxide ion catalysed phosphorylation of p-t- butylcalix [4] arene by diethyl chlorophosphate under heterogeneous conditions shows a marked sensitivity to the nature of the phase transfer catalyst used. Thus, substitution of tetraethylammonium bromide for the tetrabutylammonium bromide prescribed for the synthesis of the calixarene tetraphosphate leads to a major reaction product becoming a bis (phosphate) in which the calixarene binds as a unidentate ligand to one phosphorus and as a bidentate ligand to the other. An X-ray crystal structure analysis on this new compound shows the calixarene to adopt a somewhat distorted 'cone' conformation with an unusual orientation of one of the t-butyl substituents into the cone cavity. It also reveals that a significant diastereoselectivity must operate in the formation reaction. The only other reaction product detected in this system appears to be the calixarene tetraphosphate in a partial cone conformation.

Metal Ion Binding to Calixarenes: Pendent Arm Coordination Assisted by Self-Inclusion

1994 ◽  
Vol 47 (6) ◽  
pp. 1185 ◽  
Author(s):  
JM Harrowfield ◽  
M Mocerino ◽  
BW Skelton ◽  
CR Whitaker ◽  
AH White
Keyword(s):  
Structural Characterization ◽  
Metal Ion ◽  
Room Temperature ◽  
Ion Binding ◽  
Metal Ion Binding ◽  
Cone Conformation ◽  
X Ray ◽  
Partial Cone ◽  
Arm Coordination

The synthesis and room-temperature single-crystal X-ray structural characterization of 25,27- di(allyloxy)-5,17-di-t-butyl-26,28-dimethoxycalix[4]arene are recorded. Crystals are monoclinic, C2/c, a 29.089(5), b 10.742(2), c 26.218(8) Ǻ, β 110.09(2)°, Z = 8; the structure was refined to a residual of 0.065 for 4103 independent 'observed' [I > 3σ(I)] reflections. The flattened partial cone conformation of the molecule allows inclusion of one of the methoxy substituents in a way which could block inclusion of a metal ion capable of polyhapto aromatic coordination and which may therefore explain why solution n.m.r. measurements indicate that silver(I) binds to the pendent alkene groups.

Hydrogen-Bonded Networks Featuring Yttrium(III) Complexes of N,N’-Dimethylurea (DMU): Preparation and Characterization of [Y(DMU)6][YCl6] and [Y(NO3)3(DMU)3]

2005 ◽  
Vol 60 (4) ◽  
pp. 363-372 ◽  
Author(s):  
Athanassios K. Boudalis ◽  
Vassilios Nastopoulos ◽  
Catherine P. Raptopoulou ◽  
Aris Terzis ◽  
Spyros P. Perlepes
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Crystal Engineering ◽  
Coordination Complexes ◽  
3D Network ◽  
3D Architecture ◽  
Intramolecular Hydrogen ◽  
Hydrogen Bonded

In order to examine the possibility of using yttrium(III) in the crystal engineering of hydrogenbonded coordination complexes and to compare the molecular and supramolecular YIII/Cl3 or NO3-/DMU chemistry with the already well-developed LnIII/Cl− or NO3−/DMU chemistry (LnIII = lanthanide, DMU = N,N’-dimethylurea), compounds [Y(DMU)6][YCl6] (1) and [Y(NO3)3(DMU)3] (2) have been prepared. The structures of both compounds have been determined by single-crystal Xray diffraction. The structure of 1 consists of octahedral [Y(DMU)6]3+ and [YCl6]3− ions. The YIII ion in 2 is nine-coordinate and ligation is provided by three O-bonded DMU ligands and three bidentate chelating nitrato groups; the coordination polyhedron about the metal can be viewed as a distorted, monocapped square antiprism. The [Y(DMU)6]3+ cations and [YCl6]3− anions self-assemble to form a hydrogen-bonded 3D architecture in 1. Most of the hydrogen-bonding functionalities on the components of 2 create also a 3D network. Two motifs of interionic/intramolecular hydrogen-bonds have been observed: N-H···Cl in 1 and N-H···O(NO3−) in 2. The IR data are discussed in terms of the nature of bonding and the structures of the two complexes

Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media: Self-Assembly and Reversible Conversion of Vesicles and Gels

2011 ◽  
Vol 29 (12) ◽  
pp. 2597-2605 ◽  
Author(s):  
Ping Du ◽  
Jun Kong ◽  
Guitao Wang ◽  
Xin Zhao ◽  
Guangyu Li ◽  
...  
Keyword(s):  
Self Assembly ◽  
Aqueous Media ◽  
Supramolecular Polymers ◽  
Hydrogen Bonded
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