Non-Planar Structures of Sterically Overcrowded Trialkylamines.

Several amines with three bulky alkyl groups at the nitrogen atom, which exceed the steric crowding of triisopropylamine significantly, were synthesized, mainly by treating N-chlorodialkylamines with Grignard reagents. In six cases, namely tert-butyldiisopropylamine, 1-adamantyl-tert-butylisopropylamine, di-1-adamantylamines with an additional N-cyclohexyl or N-exo-2-norbonyl substituent, as well as 2,2,6,6-tetramethylpiperidine derivatives with N-cyclohexyl or N-neopentyl groups, appropriate single crystals were generated that enabled X-ray diffraction studies and analysis of the molecular structures. The four noncyclic amines adopt triskele-like conformations, and the sum of the three C-N-C angles is always in the range of 351.1° to 352.4°. Consequently, these amines proved to be structurally significantly flatter than trialkylamines without steric congestion, which is also signalized by the smaller heights of the NC3 pyramids (0.241-0.259 Å). There is no clear correlation between the heights of these pyramids and the degree of the steric crowding in the new amines, presumably because steric repulsion is partly compensated by dispersion interaction. In the cases of the two heterocyclic amines, the steric stress is smaller, and the molecular structures include quite different conformations. Quantum chemical calculations led to precise gas-phase structures of the sterically overcrowded trialkylamines exhibiting heights of the NC3 pyramids and preferred molecular conformers which are similar to those resulting from the X-ray studies.

Electron-rich triarylphosphines as nucleophilic catalysts for oxa-Michael reactions.

Electron-rich triarylphosphines, namely 4-(methoxyphenyl)diphenylphosphine (MMTPP) and tris(4-trimethoxyphenyl)phosphine (TMTPP), outperform commonly used triphenylphosphine (TPP) in catalyzing oxa-Michael additions. A matrix consisting of three differently strong Michael acceptors and four alcohols of varying acidity was used to assess the activity of the three catalysts. All test reactions were performed with 1 mol % catalyst loading, under solvent-free conditions and at room temperature. The results reveal a decisive superiority of TMTPP for converting poor and intermediate Michael acceptors such as acrylamide and acrylonitrile and for converting less acidic alcohols like isopropanol. With stronger Michael acceptors and more acidic alcohols, the impact of the more electron-rich catalysts is less pronounced. The experimental activity trend was rationalized by calculating the Michael acceptor affinities of all phosphine-Michael acceptor combinations. Besides this parameter, the acidity of the alcohol has a strong impact on the reaction speed. The oxidation stability of the phosphines was also evaluated and the most electron-rich TMTPP was found to be only slightly more sensitive to oxidation than TPP. Finally, the catalysts were employed in the oxa-Michael polymerization of 2-hydroxyethyl acrylate. With TMTPP polymers characterized by number average molar masses of about 1200 g/mol at room temperature are accessible. Polymerizations carried out at 80 °C resulted in macromolecules containing a considerable share of Rauhut-Currier-type repeat units and consequently lower molar masses were obtained.

Mechanistic Studies of the TRIP-Catalyzed Allylation with Organozinc Reagents.

3,3-Bis(2,4,6-triisopropylphenyl)-1,1-binaphthyl-2,2-diyl hydrogenphosphate (TRIP) catalyzes the asymmetric allylation of aldehydes with organozinc compounds, leading to highly valuable structural motifs, like precursors to lignan natural products. Our previously reported mechanistic proposal relies on two reaction intermediates and requires further investigation to really understand the mode of action and the origins of stereoselectivity. Detailed ab initio calculations, supported by experimental data, render a substantially different mode of action to the allyl boronate congener. Instead of a Brønsted acid-based catalytic activation, the chiral phosphate acts as a counterion for the Lewis acidic zinc ion, which provides the activation of the aldehyde.

Revised values for the X23 benchmark set of molecular crystals.

We present revised reference values for cell volumes and lattice energies for the widely used X23 benchmark set of molecular crystals by including the effect of thermal expansion. For this purpose, thermally-expanded structures were calculated via the quasi-harmonic approximation utilizing three dispersion-inclusive density-functional approximations. Experimental unit-cell volumes were back-corrected for thermal and zero-point energy effects, allowing now a direct comparison with lattice relaxations based on electronic energies. For the derivation of reference lattice energies, we utilized harmonic vibrational contributions averaged over four density-functional approximations. In addition, the new reference values also take the change in electronic and vibrational energy due to thermal expansion into account. This is accomplished by either utilizing experimentally determined cell volumes and heat capacities, or by relying on the quasi-harmonic approximation. The new X23b reference values obtained this way will enable a more accurate benchmark for the performance of computational methods for molecular crystals.

ZMP-SAPT: DFT-SAPT using ab initio densities.

Symmetry Adapted Perturbation Theory (SAPT) has become an important tool when predicting and analyzing intermolecular interactions. Unfortunately, Density Functional Theory (DFT)-SAPT, which uses DFT for the underlying monomers, has some arbitrariness concerning the exchange-correlation potential and the exchange-correlation kernel involved. By using ab initio Brueckner Doubles densities and constructing Kohn-Sham orbitals via the Zhao-Morrison-Parr (ZMP) method, we are able to lift the dependence of DFT-SAPT on DFT exchange-correlation potential models in first order. This way, we can compute the monomers at the coupled-cluster level of theory and utilize SAPT for the intermolecular interaction energy. The resulting ZMP-SAPT approach is tested for small dimer systems involving rare gas atoms, cations, and anions and shown to compare well with the Tang-Toennies model and coupled cluster results.

Development of Embedded and Performance of Density Functional Methods for Molecular Crystals.

We report an alternative quantum mechanical:quantum mechanical (QM:QM) method to the currently used periodic density functional calculations including dispersion and investigate its performance with respect to main structural and energetic properties of the X23 set of molecular crystals. By setting the goal of reproducing reference periodic BLYP+D3 values and by embedding BLYP+D3 into DFTB, we obtain results similar to those of periodic BLYP+D3-typically within 1-2% in lattice energies and ∼0.4% in cell volumes. The accuracy of this QM:QM method in comparison to DFTB+D and DFT+D for the X23 set of molecular crystals is discussed.

Towards hybrid density functional calculations of molecular crystals via fragment-based methods.

We introduce and employ two QM:QM schemes (a quantum mechanical method embedded into another quantum mechanical method) and report their performance for the X23 set of molecular crystals. We furthermore present the theory to calculate the stress tensors necessary for the computation of optimized cell volumes of molecular crystals and compare all results to those obtained with various density functionals and more approximate methods. Our QM:QM calculations with PBE0:PBE+D3, PBE0:PBE+MBD, and B3LYP:BLYP+D3 yield at a reduced computational cost lattice energy errors close to the ones of the parent hybrid density functional method, whereas for cell volumes, the errors of the QM:QM scheme methods are in between the generalized gradient approximation and hybrid functionals.

Efficient CO2 Insertion and Reduction Catalyzed by a Terminal Zinc Hydride Complex.

The terminal zinc hydride complex [Tntm]ZnH (2; Tntm=tris(6-tert-butyl-3-thiopyridazinyl)methanide) is an efficient hydrosilylation catalyst of CO2 at room temperature without the need of Lewis acidic additives. The inherent electrophilicity of the system leads to selective formation of the monosilylated product (MeO)3 SiO2 CH (at room temperature with a TOF of 22.2 h-1 and at 45 °C with a TOF of 66.7 h-1 ). In absence of silanes, the intermediate formate complex [Tntm]Zn(O2 CH) (3) is quantitatively formed within 5 min. All complexes were fully characterized by 1 H and 13 C NMR spectroscopy and single-crystal X-ray diffraction analyses. Density functional theory (DFT) calculations reveal a high positive charge on zinc and the increased preference of the ligand to adopt a κ3 -coordination mode.

Accurate adsorption energies for small molecules on oxide surfaces: CH4 /MgO(001) and C2 H6 /MgO(001).

A hybrid method is applied that combines second order Møller-Plesset perturbation theory (MP2) for cluster models with density functional theory for periodic (slab) models to obtain structures and energies for methane and ethane molecules adsorbed on the MgO(001) surface. Single point calculations are performed to estimate the effect of increasing the cluster size on the MP2 energies and to evaluate the difference between coupled cluster (CCSD(T)) and MP2 energies. The final estimates of the adsorption energies are 12.9 ± 1.3 and 18.9 ± 1.8 kJ/mol for CH4 and C2 H6 , respectively. © 2016 Wiley Periodicals, Inc.

Density functional theory and hydrogen bonds: are we there yet?

Density functional theory (DFT) has become more successful at introducing dispersion interactions, and can be thus applied to a wide range of systems. Amongst these are systems that contain hydrogen bonds, which are extremely important for the biological regime. Here, the description of hydrogen-bonded interactions by DFT with and without dispersion corrections is investigated. For small complexes, for which electrostatics are the determining factor in the intermolecular interactions, the inclusion of dispersion with most functionals yields large errors. Only for larger systems, in which van der Waals interactions are more important, do dispersion corrections improve the performance of DFT for hydrogen-bonded systems. None of the studied functionals, including double hybrid functionals (with the exception of DSD-PBEP86 without dispersion corrections), are more accurate than MP2 for the investigated species.

Ab Initio Study of the Adsorption of Small Molecules on Metal-Organic Frameworks with Oxo-centered Trimetallic Building Units: The Role of the Undercoordinated Metal Ion.

The interactions of H2, CO, CO2, and H2O with the undercoordinated metal centers of the trimetallic oxo-centered M3(III)(µ3-O)(X) (COO)6 moiety are studied by means of wave function and density functional theory. This trimetallic oxo-centered cluster is a common building unit in several metal-organic frameworks (MOFs) such as MIL-100, MIL-101, and MIL-127 (also referred to as soc-MOF). A combinatorial computational screening is performed for a large variety of trimetallic oxo-centered units M3(III)O (M = Al(3+), Sc(3+), V(3+), Cr(3+), Fe(3+), Ga(3+), Rh(3+), In(3+), Ir(3+)) interacting with H2O, H2, CO, and CO2. The screening addresses interaction energies, adsorption enthalpies, and vibrational properties. The results show that the Rh and Ir analogues are very promising materials for gas storage and separations.

The vibrational spectrum of FeO2(+) isomers--theoretical benchmark and experiment.

Infrared photodissociation is used to record the vibrational spectrum of FeO2 (+)(He)2-4 which shows three bands at 1035, 980, and 506 cm(-1). Quantum chemical multi-reference configuration interaction calculations (MRCISD) of structures and harmonic frequencies show that these bands are due to two different isomers, an inserted dioxo complex with Fe in the +V oxidation state and a side-on superoxo complex with Fe in the +II oxidation state. These two are separated by a substantial barrier, 53 kJ/mol, whereas the third isomer, an end-on complex between Fe(+) and an O2 molecule, is easily converted into the side-on complex. For all three isomers, states of different spin multiplicity have been considered. Our best energies are computed at the MRCISD+Q level, including corrections for complete active space and basis set extension, core-valence correlation, relativistic effects, and zero-point vibrational energy. The average coupled pair functional (ACPF) yields very similar energies. Density functional theory (DFT) differs significantly from our best estimates for this system, with the TPSS functional yielding the best results. The other functionals tested are BP86, PBE, B3LYP, TPSSh, and B2PLYP. Complete active space second order perturbation theory (CASPT2) performs better than DFT, but less good than ACPF.

Benchmarking Swaths of Intermolecular Interaction Components with Symmetry-Adapted Perturbation Theory.

A benchmark database for interaction energy components of various noncovalent interactions (NCIs) along their dissociation curve is one of the essential needs in theoretical chemistry, especially for the development of force fields and machine-learning methods. We utilize DFT-SAPT or SAPT(DFT) as one of the most accurate methods to generate an extensive stock of the energy components, including dispersion energies extrapolated to the complete basis set limit (CBS). Precise analyses of the created data, and benchmarking the total interaction energies against the best available CCSD(T)/CBS values, reveal different aspects of the methodology and the nature of NCIs. For example, error cancellation effects between the S2 approximation and nonexact xc-potentials occur, and large charge transfer energies in some systems, including heavy atoms, can explain the lower accuracy of DFT-SAPT. This method is perfect for neutral complexes containing light nonmetals, while other systems with heavier atoms should be treated carefully. In the last part, a representative data set for all NCIs is extracted from the original data.

Multimer Embedding Approach for Molecular Crystals up to Harmonic Vibrational Properties.

Accurate calculations of molecular crystals are crucial for drug design and crystal engineering. However, periodic high-level density functional calculations using hybrid functionals are often prohibitively expensive for the relevant systems. These expensive periodic calculations can be circumvented by the usage of embedding methods in which, for instance, the periodic calculation is only performed at a lower-cost level and then monomer energies and dimer interactions are replaced by those of the higher-level method. Herein, we extend such a multimer embedding approach to enable energy corrections for trimer interactions and the calculation of harmonic vibrational properties up to the dimer level. We evaluate this approach for the X23 benchmark set of molecular crystals by approximating a periodic hybrid density functional (PBE0+MBD) by embedding multimers into less expensive calculations using a generalized-gradient approximation functional (PBE+MBD). We show that trimer interactions are crucial for accurately approximating lattice energies within 1 kJ/mol and might also be needed for further improvement of lattice constants and hence cell volumes. Finally, the vibrational properties are already very well captured at the monomer and dimer level, making it possible to approximate vibrational free energies at room temperature within 1 kJ/mol.

Tunable Self-Referenced Molecular Thermometers via Manipulation of Dual Emission in Platinum(II) Pyridinedipyrrolide Complexes.

Optical temperature sensors based on self-referenced readout schemes such as the emission ratio and the decay time are crucial for a wide range of applications, with the former often preferred due to simplicity of instrumentation. This work describes a new group of dually emitting dyes, platinum(II) pincer complexes, that can be used directly for ratiometric temperature sensing without an additional reference material. They consist of Pt(II) metal center surrounded by a pyridinedipyrrolide ligand (PDP) and a terminal ligand (benzonitrile, pyridine, 1-butylimidazol or carbon monoxide). Upon excitation with blue light, these complexes exhibit green to orange emission, with quantum yields in anoxic toluene at 25 °C ranging from 13% to 86% and decay times spanning from 8.5 to 97 µs. The emission is attributed to simultaneous thermally activated delayed fluorescence (TADF) and phosphorescence processes on the basis of photophysical investigations and DFT calculations. Rather uniquely, simple manipulations in substituents of the PDP ligand and alteration of the terminal ligand allow fine-tuning of the ratio between TADF and phosphorescence from almost 100% TADF emission (Pt(MesPDPC6F5(BN)) to over 80% of phosphorescence (Pt(PhPDPPh(BuIm)). Apart from ratiometric capabilities, the complexes also are useful as decay time-based temperature indicators with temperature coefficients exceeding 1.5% K-1 in most cases. Immobilization of the dyes into oxygen-impermeable polyacrylonitrile produces temperature sensing materials that can be read out with an ordinary RGB camera or a smartphone. In addition, Pt(PhPDPPh)Py can be incorporated into biocompatible RL100 nanoparticles suitable for cellular nanothermometry, as we demonstrate with temperature measurements in multicellular colon cancer spheroids.

Ethyl acetate: X-ray, solvent and computed structures.

Ethyl acetate (ethyl ethanoate) was crystallized in situ and the crystal structure was determined. In the solid, the molecule is flat with trans conformation. The geometric details of ethyl acetate as a solvate are analyzed statistically using the Cambridge Structural Database, uncovering a high degree of hidden disorder. Despite the disorder, they exhibit a preference of the trans over the gauche isomer, with a negligible contribution of the cis isomer. These results are compared to ab initio calculations on both solid-state and molecular level. For the molecular structures, the computed energy differences of the isomers match the statistics found as a solvent. Several DFT-D2 methods used to calculate the solid state yield results that differ significantly from the experiment.

Accurate adsorption energies of small molecules on oxide surfaces: CO-MgO(001).

A hybrid MP2:DFT + D optimization method is applied using a 3 × 3 × 2 cluster model (Mg9O9) embedded in a 4 × 4 × 4 slab model. The calculated CO-Mg(2+) distance is 248 pm, and the calculated CO frequency (blue) shift is 20 cm(-1), 6 cm(-1) larger than the experimental value. For the structure obtained, MP2 calculations with basis set extrapolation on a series of cluster models of increasing size are performed. Taking into account the difference in the periodic limit at the DFT + D level, 20.9 ± 0.7 kJ mol(-1) is obtained as the estimate for the full periodic MP2 limit for the energy of CO desorption from the MgO(001) surface. CCSD(T) corrections are evaluated for the Mg9O9 cluster model using an augmented double-zeta basis set. Basis set extension effects are examined for smaller models. For a loading of Θ = 1/8, the estimated CCSD(T) value is 21.0 ± 1.0 kJ mol(-1), which is 0.4 ± 1.0 kJ mol(-1) larger than the (electronic) desorption energy derived in this study from TPD desorption barriers reported in the literature.

Directing and Understanding the Translation of a Single Molecule Dipole.

Understanding the directed motion of a single molecule on surfaces is not only important in the well-established field of heterogeneous catalysis but also for the design of artificial nanoarchitectures and molecular machines. Here, we report how the tip of a scanning tunneling microscope (STM) can be used to control the translation direction of a single polar molecule. Through the interaction of the molecular dipole with the electric field of the STM junction, it was found that both translations and rotations of the molecule occur. By considering the location of the tip with respect to the axis of the dipole moment, we can deduce the order in which rotation and translation take place. While the molecule-tip interaction dominates, computational results suggest that the translation is influenced by the surface direction along which the motion takes place.

Cross-talk between amino acid residues and flavonoid derivatives: insights into their chemical recognition.

Currently, there is a general consensus that flavonoids exert their antioxidant activity through their ability to interact with a broad range of proteins, enzymes and transcription factors rather than acting as conventional hydrogen-donating antioxidants. For this, the effect of different chemical groups of the conjugated flavonoid metabolites is apparently playing a pivotal role. Yet, many questions concerning the relevant molecular mechanisms still remain open. It is therefore crucial to gain a deeper insight into the amino acid residue-flavonoid interaction. Here we show extensive theoretical thermodynamic data and structural characteristics of the interaction of chalcone, genistein, epigallocatechin gallate, and quercetin and some of its metabolites with amino acid residues. By correlating (a) the binding energies of flavonoids-amino acid residues, (b) the hydrophobicity of amino acids, and (c) the abundance of amino acid residues in the binding sites of proteins, we can conclude that flavonoids appear to be strongly bonded to only few charged hydrophilic amino acids in the protein pockets, and rather weakly bonded to the majority of amino acid residues in the binding sites. This finding strongly impacts the understanding of the chemical recognition of flavonoids and their metabolites in their interaction with proteins and would contribute to a better design of further experimental studies. Particularly, the amino acids Phe, Leu, Ile and Trp seem to play a crucial role in the dynamics of flavonoid ligands in the binding sites of proteins.

Water as a monomer: synthesis of an aliphatic polyethersulfone from divinyl sulfone and water.

Using water as a monomer in polymerization reactions presents a unique and exquisite strategy towards more sustainable chemistry. Herein, the feasibility thereof is demonstrated by the introduction of the oxa-Michael polyaddition of water and divinyl sulfone. Upon nucleophilic or base catalysis, the corresponding aliphatic polyethersulfone is obtained in an interfacial polymerization at room temperature in high yield (>97%) within an hour. The polyethersulfone is characterized by relatively high molar mass averages and a dispersity around 2.5. The polymer was tested as a solid polymer electrolyte with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as the salt. Free-standing amorphous membranes were prepared by a melt process in a solvent-free manner. The polymer electrolyte containing 15 wt% LiTFSI featured an oxidative stability of up to 5.5 V vs. Li/Li+ at 45 °C and a conductivity of 1.45 × 10-8 S cm-1 at room temperature.