Understanding Alkene Interaction with Metal-Modified Zeolites: Thermodynamics and Mechanism of Bonding in the π-Complex.

Zeolites modified with metal cations are perspective catalysts for converting light alkenes to valuable chemicals. A crucial step of the transformation is an alkene interaction with zeolite to afford π-complex with metal cations. The mechanism of alkene bonding with cations is still unclear. To address this problem, propene adsorption on H+ (BroÌ·nsted acid site), Na+, Ca2+, Zn2+, Co2+, Cu2+, Cu+, and Ag+ cationic sites in ZSM-5 zeolite has been studied by quantum chemical calculations in terms of adsorption enthalpy, νC═C frequency, and natural bond orbital (NBO) analysis together with natural energy decomposition analysis (NEDA). It is revealed that the conventional concept of σ- and π-bonding is only partially applicable to alkene interaction with metal cations in zeolites. The orbital interaction between an alkene molecule and a metal site is more complex. Several different bonding mechanisms have been identified depending on the nature and electron configuration of the metal cation. This finding explains the complex correlations observed for propene π-complex stability and νC═C frequency shift or charge transfer from the alkene molecule. The results provide the basis for further understanding the interactions between alkenes and inorganic solid BroÌ·nsted and Lewis acids.

Enhanced Adsorption Selectivity of Carbon Dioxide and Ethane on Porous Metal-Organic Framework Functionalized by a Sulfur-Rich Heterocycle.

Porous metal-organic framework [Zn2(ttdc)2(bpy)] (1) based on thieno [3,2-b]thiophenedicarboxylate (ttdc) was synthesized and characterized. The structure contains intersected zig-zag channels with an average aperture of 4 × 6 Å and a 49% (v/v) guest-accessible pore volume. Gas adsorption studies confirmed the microporous nature of 1 with a specific surface area (BET model) of 952 m2·g-1 and a pore volume of 0.37 cm3·g-1. Extensive CO2, N2, O2, CO, CH4, C2H2, C2H4 and C2H6 gas adsorption experiments at 273 K and 298 K were carried out, which revealed the great adsorption selectivity of C2H6 over CH4 (IAST selectivity factor 14.8 at 298 K). The sulfur-rich ligands and double framework interpenetration in 1 result in a dense decoration of the inner surface by thiophene heterocyclic moieties, which are known to be effective secondary adsorption sites for carbon dioxide. As a result, remarkable CO2 adsorption selectivities were obtained for CO2/CH4 (11.7) and CO2/N2 (27.2 for CO2:N2 = 1:1, 56.4 for CO2:N2 = 15:85 gas mixtures). The computational DFT calculations revealed the decisive role of the sulfur-containing heterocycle moieties in the adsorption of CO2 and C2H6. High CO2 adsorption selectivity values and a relatively low isosteric heat of CO2 adsorption (31.4 kJ·mol-1) make the porous material 1 a promising candidate for practical separation of biogas as well as for CO2 sequestration from flue gas or natural gas.

Isomeric Scandium-Organic Frameworks with High Hydrolytic Stability and Selective Adsorption of Acetylene.

Two solvent-controlled topological isomers of scandium-organic frameworks [Sc(Hpzc)(pzc)]·DMF·2H2O (1·DMF·2H2O) and [Sc(Hpzc)(pzc)]·DMA·4H2O (2·DMA·4H2O) were synthesized using 2,5-pyrazinedicarboxylate (pzc2-) (DMF = dimethylformamide; DMA = dimethylacetamide). Despite the isomeric nature of the obtained metal-organic frameworks (MOFs), they possess different structural features and unique adsorption properties toward gases and iodine. The compound 1 has widely spread among MOF structures a dia topology with ultranarrow channels, which together with inner surface functionalization leads to enhanced CO2 adsorption and high selectivity factors in CO2/CH4 and CO2/N2 gas mixtures (25.9 and 35.6, respectively, 1/1 v/v). Moreover, a rare preferable adsorption of CO2 over C2H2 was demonstrated. The biporous isomeric framework 2 has a crb topology inherent in zeolites. A remarkable adsorption affinity to C2H2 with the ideal adsorbed solution theory selectivity factor of 127.1 for a C2H2/C2H4 mixture (1/99 v/v) was achieved for 2. Both compounds have exceptional chemical stability in a wide range of pH from acidic to basic media.

Molecular Quantum Rings Formed from a π-Conjugated Macrocycle.

The electronic structure of a molecular quantum ring (stacks of 40-unit cyclic porphyrin polymers) is characterized via scanning tunneling microscopy and scanning tunneling spectroscopy. Our measurements access the energetic and spatial distribution of the electronic states and, utilizing a combination of density functional theory and tight-binding calculations, we interpret the experimentally obtained electronic structure in terms of coherent quantum states confined around the circumference of the π-conjugated macrocycle. These findings demonstrate that large (53 nm circumference) cyclic porphyrin polymers have the potential to act as molecular quantum rings.

A Series of Mesoporous Metal-Organic Frameworks with Tunable Windows Sizes and Exceptionally High Ethane over Ethylene Adsorption Selectivity.

The NIIC-20 (NIIC stands for Nikolaev Institute of Inorganic Chemistry) is a family of five isostructural metal-organic frameworks (MOFs) based on dodecanuclear wheel-shaped carboxylate building blocks {Zn12 (RCOO)12 (glycol)6 } (glycol is deprotonated diatomic alcohol: ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol or glycerol), quantitatively crystallized from readily available starting chemicals. The crystal structures contain large mesoporous cages of 25 Šconnected through {Zn12 } rings, of which inner diameter and chemical nature depend solely on the chosen glycol. The NIIC-20 compounds feature high surface area and rarely observed inversed adsorption affinity for saturated hydrocarbon (ethane) over the unsaturated ones (ethylene, acetylene). The corresponding IAST (Ideal Adsorbed Solution Theory) adsorption selectivity factors reach as much as 15.4 for C2 H6 /C2 H4 and 10.9 for C2 H6 /C2 H2 gas mixtures at ambient conditions, exceeding those for any other porous MOF reported so far. The remarkable combination of high adsorption uptakes and high adsorption selectivities makes the NIIC-20 series a new benchmark of porous materials designed for ethylene separation applications.

Triplet Excitation and Electroluminescence from a Supramolecular Monolayer Embedded in a Boron Nitride Tunnel Barrier.

We show that ordered monolayers of organic molecules stabilized by hydrogen bonding on the surface of exfoliated few-layer hexagonal boron nitride (hBN) flakes may be incorporated into van der Waals heterostructures with integral few-layer graphene contacts forming a molecular/two-dimensional hybrid tunneling diode. Electrons can tunnel through the hBN/molecular barrier under an applied voltage VSD, and we observe molecular electroluminescence from an excited singlet state with an emitted photon energy hν > eVSD, indicating upconversion by energies up to ∼1 eV. We show that tunneling electrons excite embedded molecules into singlet states in a two-step process via an intermediate triplet state through inelastic scattering and also observe direct emission from the triplet state. These heterostructures provide a solid-state device in which spin-triplet states, which cannot be generated by optical transitions, can be controllably excited and provide a new route to investigate the physics, chemistry, and quantum spin-based applications of triplet generation, emission, and molecular photon upconversion.

The growth and fluorescence of phthalocyanine monolayers, thin films and multilayers on hexagonal boron nitride.

Free-base phthalocyanine forms distinct interfacial phases and thin films on hexagonal boron nitride including a monolayer arrangement as determined using high resolution atomic force microscopy. The phases reveal significant differences in photoluminescence with an intense peak for monolayer coverages of flat-lying molecules which is red-shifted in agreement with theoretical models.

Substrate-induced shifts and screening in the fluorescence spectra of supramolecular adsorbed organic monolayers.

We have investigated the influence of the substrate on the fluorescence of adsorbed organic molecules. Monolayer films of perylene-3,4,9,10-tetracarboxylic-3,4,9,10-diimide (PTCDI), a supramolecular network formed from PTCDI and melamine, and perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride have been deposited on hexagonal boron nitride (hBN). The principal peaks in the fluorescence spectra of these films were red-shifted by up to 0.37 eV relative to published measurements for molecules in helium droplets. Smaller shifts (∼0.03 eV) arising from interactions between neighbouring molecules are investigated by comparing the fluorescence of distinct arrangements of PTCDI, which are templated by supramolecular self-assembly and determined with molecular resolution using atomic force microscopy under ambient conditions. We compare our experimental results with red-shifts calculated using a combination of a perturbative model and density functional theory which account for, respectively, resonant and non-resonant effects of a dielectric hBN substrate. We show that the substrate gives rise to a red-shift in the fluorescence of an adsorbed molecule and also screens the interactions between neighbouring transition dipole moments; both these effects depend on the refractive index of the substrate.

A General Route to Metal-Substituted Dipnictenes of the Type [L(X)M]2 E2.

Two equivalents of LGa (L=HC[C(Me)N(2,6-iPr2 C6 H3 )]2 ) reacted with PX3 (X=Cl, Br) with insertion into two P-X bonds and formation of [L(X)Ga]2 PX (X=Cl 1, Br 2), whereas the analogous reaction with AsCl3 occurred with twofold insertion and subsequent elimination of LGaCl2 and formation of the Ga-substituted diarsene [L(Cl)Ga]2 As2 (3). Analogous findings were observed in the reactions with Me2 NAsCl2 , yielding the unsymmetrically-substituted diarsene [L(Cl)Ga]As=As[Ga(NMe2 )L] (4). The reaction of As(NMe2 )3 with LGa gave [L(Me2 N)Ga]2 As2 (5) after heating at 165 °C for five days, whereas the reaction with LAl gave [L(Me2 N)Al]2 As2 (6) after heating at only 80 °C for one day. Finally, two equivalents of LGa reacted with Bi(NEt2 )3 to give [L(Et2 N)Ga]2 Bi2 (7). Complexes 1-7 were characterized by NMR spectroscopy (1 H, 13 C, 31 P), elemental analysis, and single-crystal X-ray diffraction (except for 1 and 5). The bonding situations in 4, 6, and 7 were analyzed by quantum chemical calculations.

Synthesis, Structure, and Reactivity of Ga-Substituted Distibenes and Sb-Analogues of Bicyclo[1.1.0]butane.

Monovalent gallanediyl LGa {L=HC[C(Me)N(2,6-iPr2 C6 H3 )]2 } reacts with SbX3 to form the Ga-substituted distibenes [(LGaX)2 Sb2 ] (X=NMeEt 1, Cl 2). Upon heating, 2 reacts to the bicyclo[1.1.0]butane analogue [(LGaCl)2 (µ,η1:1 -Sb4 )] 3 containing a [Sb4 ]2- dianion. Moreover, 2 reacts with Li amides LiNR2 in salt elimination reactions that form the corresponding amido-substituted compounds 1 and [(LGaNMe2 )2 Sb2 ] 4, whereas reactions of 4 and [(LGaNMe2 )2 (µ,η1:1 -Sb4 )] 5 with two equivalents of GaCl3 resulted in the formation of 2 and 3, respectively. 1, 2 and 3 were characterized by 1 H and 13 C NMR spectroscopy, elemental analysis, and single crystal X-ray diffraction. In addition, their bonding situation was analyzed by quantum chemical calculations.

Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+ in solid phases: experimental data versus calculations.

Comparison of experimental infrared (IR) spectra of the simplest carbocations (with the weakest carborane counterions in terms of basicity, CHB11Hal11-, Hal = F, Cl) with their calculated IR spectra revealed that they are completely inconsistent, as previously reported for the t-Bu+ cation [Stoyanov E. S., et al. J. Phys. Chem. A, 2015, 119, 8619]. This means that the generally accepted explanation of hyperconjugative stabilization of the carbocations should be revised. According to the theory, one CH bond (denoted as ) from each CH3/CH2 group transfers its σ-electron density to the empty 2pz orbital of the sp2 C atom, whereas the σ-electron density on the other CH bonds of the CH3/CH2 group slightly increases. From experimental IR spectra it follows that donation of the σ-electrons from the bond to the 2pz C-orbital is accompanied by equal withdrawal of the electron density from other CH bonds, that is, the electrons are supplied from each CH bond of the CH3/CH2 group. As a result, all CH stretches of the group are red shifted, and IR spectra show typical CH3/CH2 group vibrations. Experimental findings provided another clue to the electron distribution in the hydrocarbon cations and showed that the standard computational techniques do not allow researchers to explain a number of recently established features of the molecular state of hydrocarbon cations.

Reduction of [Cp*Sb]4 with Subvalent Main-Group Metal Reductants: Syntheses and Structures of [(L1 Mg)4 (Sb4 )] and [(L2 Ga)2 (Sb4 )] Containing Edge-Missing Sb4 Units.

[Cp*Sb]4 (Cp*=C5 Me5 ) reacts with [L1 Mg]2 and L2 Ga with formation of [(L1 Mg)4 (µ4 ,η1:2:2:2 -Sb4 )] (L1 =iPr2 NC[N(2,6-iPr2 C6 H3 )]2 , 1) and [(L2 Ga)2 (µ,η2:2 -Sb4 )] (L2 =HC[C(Me)N(2,6-iPr2 C6 H3 )]2 , 2). The cleavage of the Sb-Sb and Sb-C bonds in [Cp*Sb]4 are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL1 , while 2 was formed by reductive elimination of Cp*2 and oxidative addition of L2 Ga to the Sb4 unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations.

Search for aromatic anions in the P2E3(-) (E = N, P, As, Sb, Bi) series.

We report a systematic computational study focused on the global minimum and low-lying isomer search for the P2E3(-) (E = N, P, As, Sb, Bi) series of anions. We found nine planar five-membered rings and proved their aromatic character by various quantum chemical techniques. The possible use of two different P2N3(-) aromatic anions as ligands in a number of sandwich complexes was also studied.

Synthesis and Structural Characterization of Magnesium-Substituted Polystibides [(LMg)4Sb8 ].

Redox reactions of [(L(1,2) Mg)2 ] and Sb2 R4 (R=Me, Et) yielded the first Mg-substituted realgar-type Sb8 polystibides [(L(1,2) Mg)4 (µ4 ,η(2:2:2:2) -Sb8)] (L(1) =HC[C(Me)N(2,4,6-Me3 C6 H2)]2, L(2) =HC[C(Me)N(2,6-i-Pr2 C6 H3)]2). Compounds [(L(1,2) Mg)2] serve both as reducing agents, initiating the cleavage of the Sb-C bonds, and as stabilizers for the resulting Sb8 polyanion. The polystibides were characterized by NMR and IR spectroscopies, elemental analysis, and X-ray structure analysis. In addition, results from quantum chemical calculations are presented.

Activation of C-H bond in methane by Pd atom from the bonding evolution theory perspective.

We report detailed study focused on the electron density redistribution during the simple oxidative addition reaction being the crucial stage of various catalytic processes. The bonding evolution theory based on the electron localization function and Thom's catastrophe theory shows that activation of methane's C-H bond by Pd atom consist of six elementary steps. The important feature revealed is the pronounced reorganization of Pd's outer core maxima corresponding to N-shell electrons of metal. Electronic rearrangements identified in this model reaction are likely to be the case in the more complex reactions of the same type involving transition metal compounds and, in principle, can be observed by modern ultrafast spectroscopy and diffraction techniques.

Electronic rearrangements during the inversion of lead phthalocyanine.

The mechanism of inversion of lead phthalocyanine (PbPc), possessing a shuttlecock shape, was studied in detail within the bonding evolution theory framework. We have found that reaction pathway calculated using hybrid density functional theory (DFT) method, B3LYP, consists of five structural stability domains, which are connected by four bifurcation points. Reorganization of Pb's basins with pronounced role of core ones is the basis of the catastrophes identified, whereas basins belonging to other atoms are almost not involved in the electronic structure changing. These results provide the new topological picture of processes underlying the conformational transitions of shuttlecock-shaped metal phthalocyanines adsorbed on surfaces.

Selective two-step oxidation of µ2-S ligands in trigonal prismatic unit {Re3(µ6-C)(µ2-S)3Re3} of the bioctahedral cluster anion [Re12CS17(CN)6]6­.

An oxidation of cluster anion [Re(12)CS(17)(CN)(6)](6-) by H(2)O(2) in water has been investigated. It was shown that selective two-step oxidation of bridging µ(2)-S-ligands in trigonal prismatic unit {Re(3)(µ(6)-C)(µ(2)-S)(3)Re(3)} takes place. The first stage runs rapidly, whereas the speed of the second stage depends on intensity of ultraviolet irradiation of the reaction mixture. Each stage of the reaction is accompanied by a change in the solution's color. In the first stage of the oxidation, the cluster anion [Re(12)CS(14)(SO(2))(3)(CN)(6)](6-) is produced, in which all bridging S-ligands are turned into bridging SO(2)-ligands. The second stage of the oxidation leads to formation of the anion [Re(12)CS(14)(SO(2))(2)(SO(3))(CN)(6)](6-), in which one of the SO(2)-ligands underwent further oxidation forming the bridging SO(3)-ligand. Seven compounds containing these anions were synthesized and characterized by a set of different methods, elemental analyses, IR and UV/vis spectroscopy, and quantum-chemical calculations. Structures of some compounds based on similar cluster anions, [Cu(NH(3))(5)](3)[Re(12)CS(14)(SO(2))(3)(CN)(6)]·9.5H(2)O, [Ni(NH(3))(6)](3)[Re(12)CS(14)(SO(2))(3)(CN)(6)]·4H(2)O, and [Cu(NH(3))(5)](2.6)[Re(12)CS(14)(SO(2))(3)(CN)(6)](0.6)[{Re(12)CS(14)(SO(2))(2)(SO(3))(CN)(5)(µ-CN)}{Cu(NH(3))(4)}](0.4)·5H(2)O, were investigated by X-ray analysis of single crystals.