Hydrogen-bonded Supramolecular Architectures Research Articles

Incisive analysis of hydrogen-bonded supramolecular architectures in designer polycyclitols: observation of some interesting self-assembly patterns

This article examines C–H⋯O and O–H⋯O hydrogen-bonded patterns in polyoxygenated decalins, showcasing varied supramolecular architectures influenced by oxyfunctionalisation and surrogate carbonate groups.

Polymorphism in pentaerythritol-derived ferrocenyl dithiophosphonates with intramolecular S-S coupling: a structural and computational study

Four new polymorphs (1–4) of pentaerythritol-derived ferrocenyl S-S coupled dithiophosphonates were obtained. The four polymorphs all crystallized in the monoclinic system but different space groups. Notable differences between polymorphs 3 and 4 lie in their respective unit cell parameters; a fifth polymorph 5 of the same compound crystallized in the orthorhombic system and was previously reported by us. Structural deviations between polymorphs were performed by molecular overlays and the statistical values were expressed as root mean square deviation (RMSD). The highest structural deviations were between polymorphs 1 & 4 and 2 & 4 with an RMSD of about 1.0 while polymorphs 3 & 4 had a smaller difference with an RMSD of about 0.25. The solid-state molecular organization in the five polymorphs was also studied and discussed in terms of molecular conformation, crystal packing and hydrogen-bonded networks. Polymorphs 1–5 contain a variety of intermolecular and intramolecular non-classical hydrogen bonding interactions which form hydrogen-bonded supramolecular architectures. In all polymorphs, these hydrogen bond interactions were between the hydrogen atoms of the substituted and unsubstituted ferrocenyl moiety and the adjoining sulfur atoms of the dithiophosphonate group. A DFT geometry optimization found that 2 had the lowest energy and verified the molecular overlay. The reactivity indices further proved 2 to be the most reactive.

Hydrogen-Bonded Supramolecular Architecture by Solvomorphism of Hexahydroxytriptindane: From a Rosette Network to a Rod Structure

Hydrogen-Bonded Supramolecular Architecture by Solvomorphism of Hexahydroxytriptindane: From a Rosette Network to a Rod Structure

A Flexible Microporous Hydrogen-Bonded Organic Framework

A dynamic hydrogen-bonded organic framework, HOF-12, has been synthesized from 1,3,5-tris(4-carboxyphenyl)-2,4,6-trismethylbenzene and crystallographically characterized. Through single-crystal X-ray diffraction determination, the hydrogen-bonded supramolecular architecture with a pore size of 8.6 × 10.8 A2 has been identified, which consists of six interpenetrated carboxyl-linked 6,3-topological networks. The powder X-ray diffraction analysis and the giant hysteresis sorption of carbon dioxide at 196 K demonstrate the obvious contraction of the degassed hydrogen-bonded framework, exhibiting a high CO2 uptake of 328 cm g–1 at 1.0 atm.

Hydrogen-bonded supramolecular architecture in nonlinear optical ammonium 2,4-dinitrophenolate hydrate

Single crystals of ammonium 2,4-dinitrophenolate hydrate (ADH) were grown by the slow evaporation solution growth technique. The structure is elucidated by single-crystal X-ray diffraction analysis and the crystal belongs to an orthorhombic system with noncentrosymmetric space groupPna21. The second harmonic generation efficiency of ADH is superior to that of the reference material KH2PO4. The X-ray study reveals that molecules are associated by weak C—H...O, O—H...N, N—H...π and π–π stacking interactions, which are responsible for the formation and strengthening of the supramolecular assembly. Inter- and intramolecular hydrogen-bonding interactions support the supramolecular architecture in the crystal packing. Three different types of architecture,i.e.column-like packing, a sandwich model of packing and a cluster network type of infrastructure, are observed. Optical studies reveal that the absorption is minimum in the visible region and the cutoff wavelength is at ∼240 nm. The band-gap energy was estimated by the application of the Kubelka–Munk algorithm. The powder X-ray diffraction pattern reveals the good crystallinity of the as-grown specimen. Investigation of the intermolecular interactions and crystal packing using Hirshfeld surface analysis, based on single-crystal X-ray diffraction, reveals that the close contacts are associated with molecular interactions. Fingerprint plots of Hirshfeld surfaces were used to locate and analyze the percentage of hydrogen-bonding interactions.

Electronic Deactivation of Guanosine in Extended Hydrogen-Bonded Self-Assemblies

Guanosine (G) derivatives in nonpolar aprotic solvents self-assemble to intricate hydrogen-bonded supramolecular architectures, including dimers, ribbons, and cyclic quartets. Considerable interest exists in the nature of the excited electronic states, their lifetimes and the radiationless deactivation mechanisms of the molecules in those environments. Here, we report on the electronic relaxation of G in the extended H-bridged networks in solution in n-hexane. The resulting architectures were sampled by FTIR, UV, and CD spectroscopies. The dynamics after 260 nm photoexcitation were investigated by femtosecond fluorescence up-conversion, broadband UV-vis absorption, and single-color deep-UV measurements. The observed temporal profiles reveal a hierarchy of relaxation processes, with lifetimes τ1 = 0.63 ± 0.03 ps, τ2 = 5.9 ± 0.3 ps, and τ3 = 62 ± 7 ps. Moreover, about 10% of the photoexcited molecules transform to much longer-lived product states with lifetime τ4 ≈ 3.6 ± 1.0 ns. These excited-state lifetimes are much longer than in the G monomer or the G·G dimers studied previously, hinting at sizable energy shifts among the excited ππ* and nπ* states and trapping of excited-state population in the supramolecular networks by potential energy barriers along the optimal electronic deactivation pathways of the molecules.

Construction of preorganized uracil based polytopic tectons for hydrogen-bonded supramolecular architectures

Abstract Several polytopic ligands decorated with 1-methyluracil moieties at their ends have been synthesized in high yield. Single crystal X-ray diffraction analyses of bis-uracil conjugate (bis(1-methyluracilyl-5yl-)4-nitrobenzyl methane, 2) and tetra-uracil conjugate (1,3-bis[di(1-methyluracilyl)methyl]benzene, 3) indicate presence of distinctly different hydrogen bonding patterns in the supramolecular framework. While self-assembly of 2 utilizes a wobble type (mismatch) self-pairing, no base-pairing interaction of any kind is observed in the packing of tetra-uracil conjugate 3. In the latter case, the presence of an acyclic water trimer reinforces the supramolecular framework. However, in the presence of HClO4, molecules of 3 are again associated via wobble (mismatched) complimentary self-base pairing. 3 represents the first nucleobase based tetratopic ligand till date. Investigation, as to how the hydrogen bonded supramolecular framework is affected on increasing the number of hydrogen-bonding pendants, is reported here.

Stability of Hydrogen-Bonded Supramolecular Architecture under High Pressure Conditions: Pressure-Induced Amorphization in Melamine−Boric Acid Adduct

The effects of high pressure on the structural stability of the melamine-boric acid adduct (C3N6H(6).2H3BO3, M.2B), a three-dimensional hydrogen-bonded supramolecular architecture, were studied by in situ synchrotron X-ray diffraction (XRD) and Raman spectroscopy. M.2B exhibited a high compressibility and a strong anisotropic compression, which can be explained by the layerlike crystal packing. Furthermore, evolution of XRD patterns and Raman spectra indicated that the M.2B crystal undergoes a reversible pressure-induced amorphization (PIA) at 18 GPa. The mechanism for the PIA was attributed to the competition between close packing and long-range order. Ab initio calculations were also performed to account for the behavior of hydrogen bonding under high pressure.

Diversification of Self-Organized Architectures in Supramolecular Dye Assemblies

Upon complexation with bismelamine receptors (BMn) featuring different alkyl linker lengths (number of methylene groups (n) = 5-12), a barbituric acid merocyanine dye (1) can be loaded into diverse self-organized superstructures through multiple hydrogen-bonding interactions. UV/vis, dynamic light scattering, and NMR studies in cyclohexane demonstrate that the diversification of the primarily formed hydrogen-bonded species in solution occurs by varying the linker length of BMn. Hierarchical organization of the hydrogen-bonded species is achieved by slow evaporation of the solvent (forming solvent-free films), and the resulting superstructures are evaluated by polarized optical microscopy, X-ray diffraction, SEM, and AFM techniques. The formation of columnar structures with and without two-dimensional ordering are revealed for shorter (n = 5-7) and longer (n = 11, 12) linker bis(melamines), respectively. On the contrary, in the cases of n = 8-10, the formation of lamellar structures is unveiled. Several assemblies (n = 5, 7, 11) indicate the formation of a liquid crystalline mesophase in POM and DSC analyses. Hierarchical organization is also achieved in solution by prolonged aging, affording phase-separated crystalline nanofibers (n = 5, 7) and soft nanofibrils agglomerating into wormlike objects (n = 8), gel-forming continuous globular networks (n = 10), and nanofibers (n = 11, 12). These superstructural and morphological diversifications are an outcome of the variation in the primarily formed hydrogen-bonded supramolecular architectures. Using this strategy, diverse self-assembled materials will be obtained from a single dye component.

Tailor-made naphthyridines: Self-assembling multiple hydrogen-bonded supramolecular architectures from dimer to helix

Stepwise changes of functional oxo and amino groups in 1,8-naphthyridines to modify the supramolecular architecture have been carried out. The first example of a naphthyridine helix has been found and its structure established by X-ray crystallography. The design is based on hydroxy and amido tautomeric naphthyridines which crystallize in dimers or catemers, one of them attaining helicity. The most stable tautomer present in all the compounds discussed in this paper, as well as the formation of hydrogen-bonded dimers or catemers, was established by X-ray crystallography and rationalized with theoretical calculations.

Hydrogen-Bonded Supramolecular Architectures of Organic Salts Based on Aromatic Tetracarboxylic Acids and Amines

Crystallizations of two aromatic tetracarboxylic acids, 1,4,5,8-naphthalenetetracarboxylic acid (H4NTA) and 3,4,9,10-perylenetetracarboxylic acid (H4PTA), with amines (triethylamine, TEA; ethylenediamine, EDA) in H2O give four H-bonded organic salts, [HTEA]2·[H2NTA]·2H2O (1), [HTEA]2·[H2PTA] (2), [H2EDA]2·[NTA]·3H2O (3), and [H2EDA]2·[PTA]·8H2O (4), which were structurally characterized by X-ray diffraction. In the TEA salts (1 and 2), two protons of each acid are transferred and the supramolecular H-bonded entities are generated by only acid anions (or together with H2O), whereas in 3 and 4 all four protons are transferred and both H2EDA2+ and acid anions contribute to the final framework formation, probably due to the differences in basicities of the two amines. Salt 1 has a layer structure stabilized by O−H···O H-bonds between H2O and H2NTA2- and contains a normal graph set of R24(8) (formed by two H2O and two carboxyl O atoms). Different from 1, 2 contains a 1-D structure with an R22(16) ring formed by O−H···O H-bonds between H2PTA2-. Both 3 and 4 have 3-D framework structures with well-defined 1-D channels, assembled by complicated N−H···O and O−H···O H-bonds. All the O and amino H atoms in H2EDA2+ and NTA4- or PTA4- participate in the H-bonding linkages; however both salts have great structural differences with different numbers of cocrystallized H2O. It is interesting that the 1-D channels in 3 are circular and occupied by single H2O line but those in 4 are rectangular and filled by H2O tapes with a T4(2)6(2) pattern. Herein, TEA with a larger volume and simple H-bonding manner is considered as a terminal H-bonding moiety to form low-dimensional networks, whereas EDA with favorable flexibility and various H-bonding modes is adopted to link the acid components to give higher dimensional frameworks. In addition, H4PTA seems to be proven as an interesting H-bonding molecular tecton with great potential in crystal engineering, especially for preparing materials with large cavities/channels. The stability and luminescent property of 4 have also been studied preliminarily.

Catena-Poly[[tetraaquacadmium(II)-μ-hexane-1,6-diamine-κ2N:N′] terephthalate dihydrate

The title compound, {[Cd(C6H16N2)(H2O)4](C8H4O4)·2H2O}n, (I), exhibits a chain structure. The central CdII ion is coordinated by four water molecules and two N atoms derived from two 1,6-diamino­hexane molecules, giving a zigzag-shaped polymeric chain with a [Cd—N—C—C—C—C—C—C—N]n backbone running parallel to the b axis. The two independent terephthalate anions are not coordinated to cadmium(II), acting rather as counter-ions. Each coordinated water molecule forms strong O—H⋯O hydrogen bonds with the adjacent terephthalate counter-ions, forming a three-dimensional hydrogen-bonded supramolecular architecture.

Catena-Poly[tetraaquazinc(II)-μ-benzene-1,4-dioxyacetato-κ2O:O′

In the title complex, [Zn(1,4-BDOA)(H2O)4]n or [Zn(C10H8O6)(H2O)4]n (where 1,4-BDOA2− is the benzene-1,4-dioxy­acetate dianion), the ZnII atom and the 1,4-BDOA2− ligand build up a one-dimensional polymer chain along c. The ZnII atom, located on an inversion center, shows an octahedral coordination geometry, defined by two carboxyl O atoms of different benzene-1,4-dioxy­acetate ligands and four water mol­ecules. Adjacent ZnII atoms are bridged by bis-monodentate carboxyl­ate groups of the centrosymmetric 1,4-BDOA2− ligands, to furnish the one-dimensional chain along the c axis; the Zn⋯Zn separation within the polymer is 14.717 (3) A. A hydrogen-bonded supramolecular architecture is formed via O—H⋯O intermolecular hydrogen bonds.

Hydrogen-bonded supramolecular architectures in (N-(methylpyridin-2-yl)-amidino-O-alkylurea)copper(ii) halides

Download options Please wait... Supplementary files Crystal structure data TXT (57K) Article information DOI https://doi.org/10.1039/B405875E Article type Paper Submitted 19 Apr 2004 Accepted 04 May 2004 First published 18 May 2004 Download Citation CrystEngComm, 2004,6, 159-167 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Hydrogen-bonded supramolecular architectures in (N-(methylpyridin-2-yl)-amidino-O-alkylurea)copper(II) halides U. Suksangpanya, A. J. Blake, E. L. Cade, P. Hubberstey, D. J. Parker and C. Wilson, CrystEngComm, 2004, 6, 159 DOI: 10.1039/B405875E To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Social activity Tweet Share Search articles by author Unchulee Suksangpanya Alexander J. Blake Emma L. Cade Peter Hubberstey David J. Parker Claire Wilson

Supramolecular assembly of ferrocenes via hydrogen bonds: dimensional variation in ferrocenylpyrimidine complexes with carboxylic acids and aromatic alcohols

Co-crystallization of 5-ferrocenylpyrimidine (FcPM) with various carboxylic acids and aromatic alcohols produces hydrogen-bonded supramolecular architectures. Thus, reaction of FcPM with compounds containing two hydrogen-bonding sites gives 2:1 co-crystals with discrete structures of the type [(FcPM)2·D] [where D = succinic acid (1), hydroquinone (2), resorcinol (3) and 2,2′-thiodiglycolic acid (4)]. A complex with a chiral chain structure, [FcPM·{(R)-(+)-1,1′-bi-2-naphthol}]n (5), is obtained by the combination of FcPM with (R)-(+)-1,1′-bi-2-naphthol. The binaphthol molecules form hydrogen-bonded helical chains, which carry ferrocene units as pendants. The combination of FcPM with trimesic acid and pyromellitic acid produces supramolecular complexes with tape structures, [FcPM·(trimesic acid)]n (6) and [FcPM2·(pyromellitic acid)]n (7), respectively. The tape structure of 6 consists of repeating units of large hexagonal rings while that of 7 consists of rhomboidal rings. Combination of FcPM with phloroglucinol produces a layered structure complex, [FcPM·(phloroglucinol)·2H2O]n (8), exhibiting three-dimensional hydrogen bonding. In this complex, FcPM molecules link hydrogen-bonded sheets composed of phloroglucinol and water molecules. The dimensionality of the assembled structures is influenced by the number of hydrogen-bonding substituents on the donor molecules.

Anion recognition by conservation of hydrogen-bonding patterns in salts of copper(II) co-ordinated by tetradentate bis(amidino-O-alkylurea) ligands †

Refluxing 1,2-bis(2-cyanoguanidino)ethane (L1) in methanol or ethanol containing copper(II) sulfate resulted in the formation of [CuL3m][MeOSO3]2 {L3m = [HNC(OMe)NHC(NH2)NCH2]2} and [CuL3e][EtOSO3]2 {L3e = [HNC(OEt)NHC(NH2)NCH2]2}. Structural analysis of these complexes has revealed hydrogen-bonded supramolecular architectures constructed from [CuLi]2+ cations with square planar CuN4 chromophores and [ROSO3]− anions. The basic supramolecular synthon is a 1-D chain of alternating cations and anions, a motif which is also found with Cl− and [BF2(OMe)2]− anions. The [ROSO3]− anion is an ideal fit for the space between two cations; its hydrophobic O-alkyl group is surrounded by the O-alkyl groups of the cations and its hydrophilic SO3− moiety forms N–H⋯O hydrogen bonds with their amino and imino functionalities. In [CuL3m][MeOSO3]2 the chains, which are linear, are hydrogen bonded through a second methyl sulfate anion to give a 2-D sheet motif. The sheets are bound together to form a 3-D framework through very weak Cu⋯O co-ordinative interactions which complete a tetragonally elongated octahedral geometry for the copper(II) centre. In [CuL3e][EtOSO3]2 the chains, which are sinusoidal, are hydrogen bonded through a second ethyl sulfate anion to give a bilayered arrangement. The bilayers aggregate into a 3-D framework by a combination of hydrogen bonding and weak Cu⋯O co-ordinative interactions which result in a square pyramidal co-ordination geometry for the copper(II) centre. Despite the fit between [CuLi]2+ cations and alkyl sulfate anions in the chain, when a mixture of anions (chloride and ethyl sulfate) is present in the crystallisation medium, the preferred chain supramolecular synthon of the product, [CuL3e][EtOSO3]Cl·2H2O, is that containing chloride. The ethyl sulfate anions are involved, together with water molecules, in a complex hydrogen-bonding network which connects the chains into 2-D sheets, which are assembled, in turn, into a 3-D network structure by a combination of hydrogen bonding networks and exceedingly weak Cu⋯Cl co-ordinative interactions, which give rise to a square pyramidal copper(II) co-ordination geometry.