Broadband Green Luminescence and Phase Transition in Low-Dimensional Organic-Inorganic Hybrid Iodate.

Organic-inorganic hybrid iodide systems, which can form highly ordered chromophores and uniformly oriented transition dipole moments, serve as optimal host-guest systems for the fabrication of micrometer-scale optical devices. In particular, those with low-dimensional structures can exhibit strong quantum-limited and highly localized charges, enabling the generation of high exciton energies and stable excitation emission. In this study, we report a novel instance of an organic-inorganic hybrid iodate, (C13H11N2)(IO3), which was synthesized by incorporating the optically active organic compound, 9-aminoacridine. Upon crystallization in the monoclinic space group P21/c, this compound exhibits a direct optical band gap of 2.66 eV. The incorporation of discrete organic units within the low-dimensional structures induces pronounced local charges, culminating in broadband green luminescence with a peak at 540 nm under UV excitation. This corresponds to the CIE coordinates (0.37, 0.56). A potential phase transition was inferred through a comprehensive analysis of the variable temperature structure and emission spectra. Furthermore, first-principles calculations revealed the pivotal role of organic cations in facilitating broadband luminescence.

Chiral Lead-Free Double Perovskite Single-Crystalline Microwire Arrays for Anisotropic Second-Harmonic Generation.

Halide double perovskites present a new branch for versatile optoelectronic devices because of their huge structural compatibility and environmental friendliness, whereas nonlinear optics (NLO) devices remain blank for this fascinating family. Simultaneously, the precise patterning of single-crystalline perovskite microwire arrays remains a challenge for the integration of NLO devices. Herein, we designed lead-free chiral 2D double perovskites with the nonsymmetrical structure presenting second-harmonic generation (SHG). Furthermore, perovskite single-crystalline arrays with regulated geometry, pure orientation, and high crystallinity are prepared using the capillary-bridge confined assembly technique. The efficient SHG originates from the asymmetric crystal structure and high crystallinity of the microwire arrays. Compared with their polycrystalline thin-film counterparts, linearly polarized SHG and a higher SHG conversion efficiency are demonstrated based on microwire arrays. The results not only expand the applications of lead-free double perovskites in the NLO-integrated fields but also provide a viable way for lead-free optoelectronic devices.

The Brπ halogen bond assisted self-assembly of an asymmetric molecule regulated by concentration.

The two-dimensional (2D) self-assembly behavior of an asymmetric thienophenanthrene derivative (M1) has been theoretically predicted and further probed via STM. The barely exploited Brπ halogen bonds play an assisting role in the structural formation, and a strong cooperative effect from the C-HBr bonds is shown. Such π-type halogen bond assisted self-assembly reveals self-adaption properties, which is of great interest for flexible light-emitting devices and self-healing materials.

Ordering self-assembly structures via intermolecular BrS interactions.

Recent research studies have shown that the halogenated benzo[1,2-b:4,5-b']dithiophene (DTBDT) unit as a polymer donor exhibits high charge carrier mobility due to the well-ordered molecular packing and high crystallinity, which is meaningful for achieving highly efficient organic solar cells (OSCs). However, it is difficult to acquire the accurate packing information of polymer materials. Herein, we investigated the self-assembled behaviors of two DTBDT derivatives, 4,8-bis(4-octadecylthiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (H-DTBDT) and 4,8-bis(5-bromo-4-octadecylthiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene (Br-DTBDT), to elucidate the effect of introducing a bromine atom on molecular packing structures by STM at the 1-phenyloctane/HOPG interface. It is observed that the H-DTBDT molecules exhibit a random arrangement along each lamella, while the Br-DTBDT molecules self-assemble into a highly ordered lamellar structure. Density functional theory (DFT) analysis combined with the topological properties of the electron density at the bond critical points revealed that the existence of weak intermolecular interactions of BrS facilitates the regular packing motif of Br-DTBDT molecules. The results helped us to understand that the BrS bond generally acted as the auxiliary force and can play the primary role in the construction of supramolecular nanostructures.

Chiral polymorphism in the self-assemblies of achiral molecules induced by multiple hydrogen bonds.

Owing to a wide range of applications within the areas such as chiral sensors, enantiomeric resolution, and asymmetric catalysis, understanding chiral adsorption phenomena at the interface is thereby of great importance. In particular, the role of multiple hydrogen bonds in inducing chiral diversiform morphologies has never been systematically investigated. Herein, by delicate control of the volume ratio of 1-octanoic acid and 1-octanol as the mixed solvent, a series of self-assembled nanostructures of 2-hydroxyl-7-pentadecyloxy-fluorenone (HPF) were sequentially fabricated, including the achiral densely-packed pattern, the chiral "6-2" pattern, the chiral alternate pattern, and the chiral double-rosette pattern. Eventually, those patterns would evolve into an achiral and thermodynamically favored zigzag pattern. Based on DFT calculations, we demonstrate that the stabilities of diversiform morphologies originate from different hydrogen bonding and molecular packing densities. In addition, quantum theory of atoms in molecule (QTAIM) analysis is further applied to interpret the nature of these hydrogen bonds.

Cooperating dipole-dipole and van der Waals interactions driven 2D self-assembly of fluorenone derivatives: ester chain length effect.

Two-dimensional supramolecular assemblies of a series of 2,7-bis(10-n-alkoxycarbonyl-decyloxy)-9-fluorenone derivatives (BAF-Cn, n = 1, 3-6) consisting of polar fluorenone moieties and ester alkoxy chains were investigated by scanning tunneling microscopy on highly oriented pyrolytic graphite surfaces. The chain-length effect was observed in the self-assembly of BAF-Cn. Self-assembly of BAF-C1 was composed of a linear I pattern, where the side chains adopted a fully interdigitated arrangement. As the length of side chains increased, the coexistence of a linear I pattern and a cyclic pattern for the self-assembly of BAF-C3 was observed. Upon increasing the length of the alkoxy chain even further (n = 4-6), another linear II structure was observed in the BAF-Cn monolayer, in which the side chains in adjacent rows were arranged in a tail-to-tail configuration. It is reasonable to conclude that not only the van der Waals forces but also the dipole-dipole interactions from both the fluorenone cores and the ester alkoxy chains play critical roles in the self-assemblies of BAF-Cn. Our work provides detailed insights into the effect of intermolecular dipole-dipole and van der Waals interactions on the monolayer morphology of fluorenone derivatives.

Halogen bonding versus hydrogen bonding induced 2D self-assembled nanostructures at the liquid-solid interface revealed by STM.

We design a bifunctional molecule (5-bromo-2-hexadecyloxy-benzoic acid, 5-BHBA) with a bromine atom and a carboxyl group and its two-dimensional self-assembly is experimentally and theoretically investigated by using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The supramolecular self-organization of 5-BHBA in two different solvents (1-octanoic acid and n-hexadecane) at the liquid-solid interface at different solution concentrations is obviously different due to the cooperative and competitive intermolecular halogen and hydrogen bonds. Three kinds of nanoarchitectures composed of dimers, trimers and tetramers are formed at the 1-octanoic acid/graphite interface based on -COOHHOOC-, triangular C[double bond, length as m-dash]OBrH-C, -BrO(H), BrBr, and OH interactions. Furthermore, by using n-hexadecane as the solvent, two kinds of self-assembled linear patterns can be observed due to the coadsorption, in which the dimers are formed by intermolecular -COOHHOOC- hydrogen bonds. The molecule-solvent and solvent-solvent van der Waals force and intermolecular hydrogen bonds dominate the formation of coadsorbed patterns. We propose that the cooperative and competitive halogen and hydrogen bonds are related to the polarity of the solvent and the type of molecule-solvent interaction. The intermolecular binding energy of different dimers and their stability are supported by theoretical calculations. The result provides a new and innovative insight to induce the 2D self-assembled nanostructures by halogen and hydrogen bonds at the liquid-solid interface.

Cooperation and competition between halogen bonding and van der Waals forces in supramolecular engineering at the aliphatic hydrocarbon/graphite interface: position and number of bromine group effects.

Herein, the photophysical properties of two π-conjugated thienophenanthrene derivatives (6,9- and 5,10-DBTD) are reported. Their self-assembled monolayers in aliphatic hydrocarbon solvents under different concentrations were investigated by scanning tunneling microscopy on a graphite surface. The STM results revealed that the self-assembled structures of the two geometrical isomers exhibited absolutely different behaviors. At the aliphatic solvent/graphite interface, 6,9-DBTD produced almost a single stable coassembled linear structure, except for that with n-tridecane as the solvent. However, the self-assembly of 5,10-DBTD showed structural diversity, and it presented a gradient variety through increasing the chain length of the aliphatic solvents as well as the solution concentration. All ordered self-assembled adlayers critically depend on not only the interchain van der Waals (vdW) interactions, but also on multiple intermolecular interactions, including BrO[double bond, length as m-dash]C and BrS hetero-halogen bonds, homo-BrBr interactions, and HBr and HO hydrogen bonds. We proposed that the cooperation and competition of the intermolecular interactions involving a Br atom and interchain vdW forces induce this structural variety. Density functional theory calculations support to unravel the different elementary structural units based on halogen bonds and hydrogen bonds and were useful tools to dissect and explain the formation mechanism.

Controllable Orientation of Ester-Group-Induced Intermolecular Halogen Bonding in a 2D Self-Assembly.

Halogen bonding with high specificity and directionality in the geometry has proven to be an important type of noncovalent interaction to fabricate and control 2D molecular architectures on surfaces. Herein, we first report how the orientation of the ester substituent for thienophenanthrene derivatives (5,10-DBTD and 5,10-DITD) affects positive charge distribution of halogens by density functional theory, thus determining the formation of an intermolecular halogen bond and different self-assembled patterns by scanning tunneling microscopy. The system presented here mainly includes heterohalogen X···O═C and X···S halogen bonds, H···Br and H···O hydrogen bonds, and I···I interaction, where the directionality and strength of such weak bonds determine the molecular arrangement by varying the halogen substituent. This study provides a detailed understanding of the role of ester orientation, concentration, and solvent effects on the formation of halogen bonds and proves relevant for identification of multiple halogen bonding in supramolecular chemistry.