Supplementary data for article: Chongboriboon, N.; Samakun, K.; Inprasit, T.; Kielar, F.; Dungkaew, W.; Wong, L. W.-Y.; Sung, H. H.-Y.; Ninković, D. B.; Zarić, S. D.; Chainok, K. Two-Dimensional Halogen-Bonded Organic Frameworks Based on the Tetrabromobenzene-1,4-Dicarboxylic Acid Building Molecule. CrystEngComm 2019, 22 (1), 24–34. https://doi.org/10.1039/c9ce01140d

Supplementary material for: [https://doi.org/10.1039/c9ce01140d]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/3795

Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores

Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control

Halogen-Bonding-Driven Self-Assembly of Solvates of Tetrabromoterephthalic Acid

Halogen bonding is one of the most interesting noncovalent attractions capable of self-assembly and recognition processes in both solution and solid phase. In this contribution, we report on the formation of two solvates of tetrabromoterephthalic acid (H2Br4tp) with acetonitrile (MeCN) and methanol (MeOH) viz. H2Br4tp·2MeCN (1MeCN) and H2Br4tp·2MeOH (2MeOH). The host structures of both 1MeCN and 2MeOH are assembled via the occurrence of simultaneous Br···Br, Br···O, and Br···π halogen bonding interactions, existing between the H2Br4tp molecular tectons. Among them, the cooperative effect of the dominant halogen bond in combination with hydrogen bonding interactions gave rise to different supramolecular assemblies, whereas the strength of the halogen bond depends on the type of hydrogen bond between the molecules of H2Br4tp and the solvents. These materials show a reversible release/resorption of solvent molecules accompanied by evident crystallographic phase transitions

Self-Assembly of 1D Double-Chain and 3D Diamondoid Networks of Lanthanide Coordination Polymers through In Situ-Generated Ligands: High-Pressure CO2 Adsorption and Photoluminescence Properties

Two new lanthanide-based coordination polymers, [Sm2(bzz)(ben)6(H2O)3]·0.5H2O (1) and [Eu(bbz)(ben)3] (2), were synthesized and characterized. The described products were formed from in situ-generated benzoate (ben) and N’-benzoylbenzohydrazide (bbz) ligands, which were the products of transformation of originally added benzhydrazide (bzz) under hydrothermal conditions. Compound 1 exhibits a one-dimensional (1D) double-chain structure built up from the connection of the central Sm3+ ions with a mixture of bzz and ben ligands. On the other hand, 2 features a 3D network with a 4-connected (66) dia topology constructed from dinuclear [Eu2(ben)6] secondary building units and bbz linkers. High-pressure CO2 sorption studies of activated 1 show that maximum uptake increases to exceptionally high values of 376.7 cm3 g−1 (42.5 wt%) under a pressure of 50 bar at 298 K with good recyclability. Meanwhile, 2 shows a typical red emission in the solid state at room temperature with the decay lifetime of 1.2 ms

Two-dimensional halogen-bonded organic frameworks based on the tetrabromobenzene-1,4-dicarboxylic acid building molecule

Two-dimensional (2D) halogen-bonded organic frameworks were readily engineered by strong and directional effects of the primary Br⋯O and the secondary Br⋯π halogen bonding interactions from the tetrabromobenzene-1,4-dicarboxylic acid (H2Br4BDC) building molecule involving 100% supramolecular yields. The 2D assembly can function as a host layered framework for the intercalation of various guest solvents including acetone (ATN), ethanol (EtOH), dimethyl sulfoxide (DMSO), and ethylene glycol (EG) resulting in a 1 : 2 host : guest complexation stoichiometry viz. H2Br4BDC·2S (S = ATN (1ATN), EtOH (2EtOH), DMSO (3DMSO), and EG (4EG)). All the solvates show remarkable similarities in their 2D layered sheets and the bilayer distance significantly responds to the size, shape, molecular conformation, and strength of the hydrogen bonding capability of the intercalated solvent molecules. The transition between solvate formation and desolvation was found to be facile and reversible upon the desolvation-resolvation process. The estimated Br⋯O halogen bonding energy of the solvates is in the -0.6 to -1.7 kcal mol-1 range, which was determined by quantum-mechanical calculations based on density functional theory (DFT) calculations. Furthermore, to quantitatively identify the host-guest intermolecular interactions of these solvates, they were visually compared by Hirshfeld surface analysis.Supplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/3796