Investigation of Guest-Induced Flexibility in Pyrazine Derivative of ALFFIVE MOF via Molecular Simulation.

One of the important understandings of porous solids like metal-organic frameworks (MOFs) is their flexibility. Therefore, there are certain computational studies on flexible MOFs in the literature, primarily concentrating on MIL-53, UiO-66, and DUT-49. Here, investigation of another class of MOF, that is, [Ni(1,4-pyrazine)2(AlF5)]n, was shown to have guest-induced flexible characteristics; nevertheless, the mechanism for the emergence of flexibility is uncertain. We simulated the structural flexibility of [Ni(1,4-pyrazine)2(AlF5)]n, named ALFFIVE-Ni-pyr-TBP, upon adsorption of a guest molecule based on force fields using the molecular dynamics (MD) method and Monte Carlo (MC) simulations. As the first step towards understanding guest-induced flexibility, the MC simulations were performed by relaxing the framework and then further comparing it with the rigid framework. Subsequently, MD simulations were executed on the ALFFIVE-Ni-pyr-TBP framework with and without the guest molecules. In the case of moisture adsorption, the MOF system was identified to undergo a geometric transformation from trigonal bipyramidal to square bipyramidal geometry due to the strong interaction of oxygen of the water with the metal aluminum. However, some tilting in the pyrazine ligand was observed in the presence of all the guest molecules. Therefore, the detailed guest-induced flexibility described in this work could support the ALFFIVE series to be explored for future adsorption applications.

Oxidation State-Dependent Electronic Properties of Sulfur-Containing Thermally Activated Delayed Fluorescence Molecules.

Comparative studies of a series of sulfur-containing thermally activated delayed fluorescence (TADF) molecules and their oxidized compounds are carried out by means of electronic structure calculations. Aiming at investigating the effects of oxidation of bridged sulfur on the modulation of electronic structures of sulfur-containing TADF molecules, their geometrical structures, singlet (S1) and triple (T1) energies and their gap (ΔEST), the transition dipole moment, the spin-orbit coupling (SOC) between S1 and T1 states, the ionization potentials, and electron affinities are analyzed in detail to determine the structure-property relationships in these investigated TADF molecules and their corresponding oxidized counterparts. The electronic structure calculations show that the oxidation of bridged sulfur into the corresponding sulfoxide and sulfone significantly changes the electronic properties of TADF molecules. Interestingly, a substantial reduction in the singlet-triplet energy difference is possible with an increase in the oxidation state of the sulfur atom in the core. Moreover, the sulfone-containing molecules exhibit both S1 and T1 states having a large charge transfer (CT) excitation characteristic, which helps reduce the singlet-triplet energy gap and facilitates the reverse intersystem crossing (RISC) from the triplet state to the singlet state. SOC values increase with an increase in the oxidation state of the sulfur atom. Particularly, a sulfoxide-containing core moiety exhibits higher SOC values when compared with the sulfone-containing acceptor core.

The role of sulfur oxidation in controlling the electronic properties of sulfur-containing host molecules for phosphorescent organic light-emitting diodes.

In this study a series of dibenzothiophene (DBT) derivatives having different valence states of sulfur atoms have been reported as host materials for blue phosphorescent organic light-emitting diodes. Their electronic properties have also been thoroughly investigated to develop structure-property relationships which include the consideration of the effect of various oxidation states of the sulfur atom in the core moiety and linking (C-N linkage) of subunits with the core at different positions. The results obtained from the electronic structure calculations highlight that the triplet energy (ET), singlet-triplet energy difference (ΔEST), reorganization energy for the hole and the injection barrier for the electron decrease with an increase in the oxidation state of the sulfur atom in DBT. On the other hand, the injection barrier for the hole and the reorganization energy for the electron increase upon increasing the oxidation state of the sulfur atom present in the DBT.

A Highly Selective Chemosensor for Cyanide Derived from a Formyl-Functionalized Phosphorescent Iridium(III) Complex.

A new phosphorescent iridium(III) complex, bis[2',6'-difluorophenyl-4-formylpyridinato-N,C4']iridium(III) (picolinate) (IrC), was synthesized, fully characterized by various spectroscopic techniques, and utilized for the detection of CN(-) on the basis of the widely known hypothesis of the formation of cyanohydrins. The solid-state structure of the developed IrC was authenticated by single-crystal X-ray diffraction. Notably, the iridium(III) complex exhibits intense red phosphorescence in the solid state at 298 K (ΦPL = 0.16) and faint emission in acetonitrile solution (ΦPL = 0.02). The cyanide anion binding properties with IrC in pure and aqueous acetonitrile solutions were systematically investigated using two different channels: i.e., by means of UV-vis absorption and photoluminescence. The addition of 2.0 equiv of cyanide to a solution of the iridium(III) complex in acetonitrile (c = 20 µM) visibly changes the color from orange to yellow. On the other hand, the PL intensity of IrC at 480 nm was dramatically enhanced ∼5.36 × 10(2)-fold within 100 s along with a strong signature of a blue shift of the emission by ∼155 nm with a detection limit of 2.16 × 10(-8) M. The cyanohydrin formation mechanism is further supported by results of a (1)H NMR titration of IrC with CN(-). As an integral part of this work, phosphorescent test strips have been constructed by impregnating Whatman filter paper with IrC for the trace detection of CN(-) in the contact mode, exhibiting a detection limit at the nanogram level (∼265 ng/mL). Finally, density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed to understand the electronic structure and the corresponding transitions involved in the designed phosphorescent iridium(III) complex probe and its cyanide adduct.

Monolayer to interdigitated partial bilayer smectic C transition in thiophene-based spacer mesogens: X-ray diffraction and (13)C nuclear magnetic resonance studies.

Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state (13)C NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

Structural investigation of resorcinol based symmetrical banana mesogens by XRD, NMR and polarization measurements.

Synthesis and structural characterization of two novel symmetrical banana mesogens built from resorcinol with seven phenyl rings linked by ester and imine with a terminal dodecyl/dodecyloxy chain has been carried out. Density functional theory (DFT) has been employed for obtaining the geometry optimized structures, the dipole moments and (13)C NMR chemical shifts. The HOPM and DSC studies revealed enantiotropic B2 and B7 phases for the dodecyl and dodecyloxy homologs respectively. The powder X-ray studies of both the mesogens indicate the presence of layer ordering. The polarization measurements reveal an anti-ferroelectric switching for the B2 phase of the dodecyl homolog whose structure has been identified as SmCSPA. The B7 phase of the dodecyloxy homolog was found to be non-switchable. High resolution (13)C NMR study of the dodecyl homolog in its mesophase has been carried out. (13)C-(1)H dipolar couplings obtained from the 2-dimensional separated local field spectroscopy experiment were used to obtain the orientational order parameters of the different segments of the mesogen. Very large (13)C-(1)H dipolar couplings observed for the carbons of the central phenyl ring (9.7-12.3 kHz) in comparison to the dipolar couplings of those of the side arm phenyl rings (less than 3 kHz) are a direct consequence of the ordering in the banana phase and the shape of the molecule. From the ratio of the local order parameter values, the bent-angle of the mesogen could be determined in a straight forward manner to be 120.5°.