Hydrogen-Bonded Organic Frameworks: Structural Design and Emerging Applications.

Constructing well-organized organic frameworks with tailor-made functionalities potentially boost multi-domain applications. Hydrogen bonding (H-bonding) is a category of general and weak intermolecular interactions when compared with covalent bonding or metal-ligand coordination. Porous frameworks mainly assembled by H-bonding (named hydrogen-bonded organic frameworks, HOFs) are intrinsically capable of decomposing and regenerating, a distinctive advantage to improve their processability while expanding the applicability. This paper summarizes the basic building concepts of HOFs, including feasible hydrogen bonded motifs, effective molecular structures, and their emerging applications.

Supramolecular cis-"Bis(Chelation)" of [M(CN)6]3- (M = CrIII, FeIII, CoIII) by Phloroglucinol (H3PG).

Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1-3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3-;(H3PG)2}∞ network features original {[M(CN)6]3-;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)2Ar, {[M(CN)6]3-;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3- and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)6]3-;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

Molecular Tectonics with Di- and Trinuclear Organotin Compounds.

Di- and trinuclear organotin(IV) complexes, in which the metal atoms are separated by large aromatic connectors, are useful building blocks for self-assembly. This is demonstrated by the preparation of [1+1], [2+2], and [2+3] macrocyclic and cage-type structures in combination with organic aromatic dicarboxylates. The linkage of the metal atoms by organic binders and the option of varying the number of reactive M-X sites generate versatile building blocks enabling molecular tectonics instead of the node-based strategy generally employed in metallo-supramolecular self-assembly.

Surface-confined self-assembled Janus tectons: a versatile platform towards the noncovalent functionalization of graphene.

A general strategy for simultaneously generating surface-based supramolecular architectures on flat sp(2) -hybridized carbon supports and independently exposing on demand off-plane functionality with controlled lateral order is highly desirable for the noncovalent functionalization of graphene. Here, we address this issue by providing a versatile molecular platform based on a library of new 3D Janus tectons that form surface-confined supramolecular adlayers in which it is possible to simultaneously steer the 2D self-assembly on flat C(sp(2))-based substrates and tailor the external interface above the substrate by exposure to a wide variety of small terminal chemical groups and functional moieties. This approach is validated throughout by scanning tunneling microscopy (STM) at the liquid-solid interface and molecular mechanics modeling studies. The successful self-assembly on graphene, together with the possibility to transfer the graphene monolayer onto various substrates, should considerably extend the application of our functionalization strategy.

Synthesis of Mono-, Di-, Tri-, and Tetra-cationic Pyridinium and Vinylpyridinium Modified [2.2]Paracyclophanes: Modular Receptors for Supramolecular Systems.

In this report, a new series of mono-, di-, tri-, and tetra-cationic pyridinium and vinyl pyridinium-modified [2.2]paracyclophanes as useful molecular tectons for supramolecular systems are described. Regioselective functionalization at specific positions, followed by resolution step and successive transformations through Pd-catalyzed Suzuki-Miyaura and Mizoroki-Heck cross-coupling chemistry furnish a series of modular PCP scaffolds. In our proof-of-concept study, on N-methylation, the PCPs bearing (cationic) pyridyl functionalities were demonstrated as useful molecular receptors in host-guest supramolecular assays. The PCPs on grafting with light-responsive azobenzene (-N=N-) functional core as side-groups impart photosensitivity that can be remotely transformed on irradiation, offering photo-controlled smart molecular functions. Furthermore, the symmetrical PCPs bearing bi-, and tetra-pyridyl functionalities at the peripheries have enormous potential to serve as ditopic and tetratopic 3D molecular tectons for engineering non-covalent supramolecular assemblies with new structural and functional attributes.

Porous Cationic Covalent Triazine-Based Frameworks as Platforms for Efficient CO2 and Iodine Capture.

Porous cationic covalent triazine-based frameworks (CTFs) with imidazolium salts as tectons were prepared via ionothermal synthesis. The high-PF6 - -content CTF shows the CO2 adsorption of 44.7 cm3 g-1 and I2 capture capacity of 312 wt %. The influence of counterion species and contents on the porosities, CO2 adsorptions, and I2 capture capacities of the CTFs has been investigated.