Contrasting packing modes for tubular assemblies in chlorosomes.

The largest light-harvesting antenna in nature, the chlorosome, is a heterogeneous helical BChl self-assembly that has evolved in green bacteria to harvest light for performing photosynthesis in low-light environments. Guided by NMR chemical shifts and distance constraints for Chlorobaculum tepidum wild-type chlorosomes, the two contrasting packing modes for syn-anti parallel stacks of BChl c to form polar 2D arrays, with dipole moments adding up, are explored. Layered assemblies were optimized using local orbital density functional and plane wave pseudopotential methods. The packing mode with the lowest energy contains syn-anti and anti-syn H-bonding between stacks. It can accommodate R and S epimers, and side chain variability. For this packing, a match with the available EM data on the subunit axial repeat and optical data is obtained with multiple concentric cylinders for a rolling vector with the stacks running at an angle of 21° to the cylinder axis and with the BChl dipole moments running at an angle ߠ∼ 55° to the tube axis, in accordance with optical data. A packing mode involving alternating syn and anti parallel stacks that is at variance with EM appears higher in energy. A weak cross-peak at -6 ppm in the MAS NMR with 50 kHz spinning, assigned to C-181, matches the shift of antiparallel dimers, which possibly reflects a minor impurity-type fraction in the self-assembled BChl c.

Unveiling the topology of partially disordered micro-crystalline nitro-perylenediimide with X-aggregate stacking: an integrated approach.

Profound knowledge of the molecular structure and supramolecular organization of organic molecules is essential to understand their structure-property relationships. Herein we demonstrate the packing arrangement of partially disordered nitro-perylenediimide (NO2-PDI), revealing that the perylenediimide units exhibit an X-shaped packing pattern. The packing of NO2-PDI is derived using a complementary approach that utilises solid-state NMR (ssNMR) and 3D electron diffraction (3D ED) techniques. Perylenediimide (PDI) molecules are captivating due to their high luminescence efficiency and optoelectronic properties, which are related to supramolecular self-assembly. Increasing the alkyl chain length on the imide substituent poses a more significant challenge in crystallizing the resulting molecule. In addition to the alkyl tails, other functional groups, like the nitro group attached as a bay substituent, can also cause disorder. Such heterogeneity could lead to diffuse scattering, which then complicates the interpretation of diffraction experiment data, where perfect periodicity is expected. As a result, there is an unmet need to develop a methodology for solving the structures of difficult-to-crystallize materials. A synergistic approach is utilised in this manuscript to understand the packing arrangement of the disordered material NO2-PDI by making use of 3D ED, ssNMR and density functional theory calculations (DFT). The combination of these experimental and theoretical approaches provides great promise in enabling the structural investigation of novel materials with customized properties across various applications, which are, due to the internal disorder, very difficult to study by diffraction techniques. By effectively addressing these challenges, our methodology opens up new avenues for material characterization, thereby driving exciting advancements in the field.

The Effect of Disorder on Endogenous MAS-DNP: Study of Silicate Glasses and Crystals.

In dynamic nuclear polarization nuclear magnetic resonance (DNP-NMR) experiments, the large Boltzmann polarization of unpaired electrons is transferred to surrounding nuclei, leading to a significant increase in the sensitivity of the NMR signal. In order to obtain large polarization gains in the bulk of inorganic samples, paramagnetic metal ions are introduced as minor dopants acting as polarizing agents. While this approach has been shown to be very efficient in crystalline inorganic oxides, significantly lower enhancements have been reported when applying this approach to oxide glasses. In order to rationalize the origin of the difference in the efficiency of DNP in amorphous and crystalline inorganic matrices, we performed a detailed comparison in terms of their magnetic resonance properties. To diminish differences in the DNP performance arising from distinct nuclear interactions, glass and crystal systems of similar compositions were chosen, Li2OCaO·2SiO2 and Li2CaSiO4, respectively. Using Gd(III) as polarizing agent, DNP provided signal enhancements in the range of 100 for the crystalline sample, while only up to around factor 5 in the glass, for both 6Li and 29Si nuclei. We find that the drop in enhancement in glasses can be attributed to three main factors: shorter nuclear and electron relaxation times as well as the dielectric properties of glass and crystal. The amorphous nature of the glass sample is responsible for a high dielectric loss, leading to efficient microwave absorption and consequently lower effective microwave power and an increase in sample temperature which leads to further reduction of the electron relaxation time. These results help rationalize the observed sensitivity enhancements and provide guidance in identifying materials that could benefit from the DNP approach.

Endogenous Dynamic Nuclear Polarization for Sensitivity Enhancement in Solid-State NMR of Electrode Materials.

Rational design of materials for energy storage systems relies on our ability to probe these materials at various length scales. Solid-state NMR spectroscopy is a powerful approach for gaining chemical and structural insights at the atomic/molecular level, but its low detection sensitivity often limits applicability. This limitation can be overcome by transferring the high polarization of electron spins to the sample of interest in a process called dynamic nuclear polarization (DNP). Here, we employ for the first time metal ion-based DNP to probe pristine and cycled composite battery electrodes. A new and efficient DNP agent, Fe(III), is introduced, yielding lithium signal enhancement up to 180 when substituted in the anode material Li4Ti5O12. In addition for being DNP active, Fe(III) improves the anode performance. Reduction of Fe(III) to Fe(II) upon cycling can be monitored in the loss of DNP activity. We show that the dopant can be reactivated (return to Fe(III)) for DNP by increasing the cycling potential window. Furthermore, we demonstrate that the deleterious effect of carbon additives on the DNP process can be eliminated by using carbon free electrodes, doped with Fe(III) and Mn(II), which provide good electrochemical performance as well as sensitivity in DNP-NMR. We expect that the approach presented here will expand the applicability of DNP for studying materials for frontier challenges in materials chemistry associated with energy and sustainability.

B-MWW Zeolite: The Case Against Single-Site Catalysis.

Boron-containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron-containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B2 (OH)x O(3-x/2) (x=0-6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM-22 isomorphously substituted with boron (B-MWW). Using 11 B solid-state NMR spectroscopy, we show that the majority of boron species in B-MWW exist as isolated BO3 units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B-MWW for ODH of propane falsifies the hypothesis that site-isolated BO3 units are the active site in boron-based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium-based catalysts and provides an important piece of the mechanistic puzzle.

Ambient synthesis of nanomaterials by in situ heterogeneous metal/ligand reactions.

Coordination polymers are ideal synthons in creating high aspect ratio nanostructures, however, conventional synthetic methods are often restricted to batch-wise and costly processes. Herein, we demonstrate a non-traditional, frugal approach to synthesize 1D coordination polymers by in situ etching of zerovalent metal particle precursors. This procedure is denoted as the heterogeneous metal/ligand reaction and was demonstrated on Group 13 metals as a proof of concept. Simple carboxylic acids supply the etchant protons and ligands for metal ions (conjugate base) in a 1 : 1 ratio. This scalable reaction produces a 1D polymer that assembles into high-aspect ratio 'nanobeams'. We demonstrate control over crystal structure and morphology by tuning the: (i) metal center, (ii) stoichiometry and (iii) structure of the ligands. This work presents a general scalable method for continuous, heat free and water-based coordination polymer synthesis.

Probing the Transformation of Boron Nitride Catalysts under Oxidative Dehydrogenation Conditions.

Hexagonal boron nitride (h-BN) and boron nitride nanotubes (BNNT) were recently reported as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins in the gas phase. Previous studies revealed a substantial increase in surface oxygen content after exposure to ODH conditions (heating to ca. 500 °C under a flow of alkane and oxygen); however, the complexity of these materials has thus far precluded an in-depth understanding of the oxygenated surface species. In this contribution, we combine advanced NMR spectroscopy experiments with scanning electron microscopy and soft X-ray absorption spectroscopy to characterize the molecular structure of the oxygen functionalized phase that arises on h-BN and BNNT following catalytic testing for ODH of propane. The pristine BN materials are readily oxidized and hydrolyzed under ODH reaction conditions to yield a phase consisting of three-coordinate boron sites with variable numbers of hydroxyl and bridging oxide groups which is denoted B(OH) xO3- x (where x = 0-3). Evidence for this robust oxide phase revises previous literature hypotheses of hydroxylated BN edges as the active component on h-BN.

A Molecular Level Approach To Elucidate the Supramolecular Packing of Light-Harvesting Antenna Systems.

The molecular geometry and supramolecular packing of two bichromophoric prototypic light harvesting compounds D1A2 and D2A2, consisting of two naphthylimide energy donors that were attached to the 1,7 bay positions of a perylene monoimide diester energy acceptor, have been determined by a hybrid approach using magic angle spinning NMR spectroscopy and electron nano-crystallography (ENC), followed by modelling. NMR shift constraints, combined with the P 1 ‾ space group obtained from ENC, were used to generate a centrosymmetric dimer of truncated perylene fragments. This racemic packing motif is used in a biased molecular replacement approach to generate a partial 3D electrostatic scattering potential map. Resolving the structure of the bay substituents is guided by the inversion symmetry, and the distance constraints obtained from heteronuclear correlation spectra. The antenna molecules form a pseudocrystalline lattice of antiparallel centrosymmetric dimers with pockets of partially disordered bay substituents. The two molecules in a unit cell form a butterfly-type arrangement. The hybrid methodology that has been developed is robust and widely applicable for critical structural underpinning of self-assembling structures of large organic molecules.

Determination of Controlled Self-Assembly of a Paracrystalline Material by Homology Modelling with Hybrid NMR and TEM.

Controlling complexity, flexibility, and functionality of synthetic and biomimetic materials requires insight into how molecular functionalities can be exploited for steering their packing. A fused NDI-salphen (NDI=naphthalene diimide) prototypic artificial photosynthesis material, DATZnS, is shown to be comprised of a phenazine motif, in which the alignment of electric dipole moments in a P2/c supramolecular scaffold can be modulated with bulky substituents. They can also be switched between parallel stacks of dipoles running antiparallel in the DATZnS-H compared with parallel stacks of dipoles in polar layers running in opposite directions in the DATZnS(3'-NMe) parent compound. Spatial correlations obtained from HETCOR spectra, collected with a long cross polarization contact time of 2 ms, reveal an antiparallel stacking for the DATZnS-H homologue. These constraints and limited data from TEM are used to construct a structural model within the P2/c space group determined by the molecular C2 symmetry. By using homology modelling, a pseudo octahedral coordination of the Zn is shown to follow the packing-induced chirality with enantiomeric pairs of the Λ and Δ forms alternating along antiparallel stacks. The model helps to understand how the steric hindrance modulates the self-assembly in this novel class of fused materials by steric hindrance at the molecular level.

A Hybrid Solid-State NMR and Electron Microscopy Structure-Determination Protocol for Engineering Advanced para-Crystalline Optical Materials.

Hybrid magic-angle spinning (MAS) NMR spectroscopy and TEM were demonstrated for de novo structure determination of para-crystalline materials with a bioinspired fused naphthalene diimide (NDI)-salphen-phenazine prototype light-harvesting compound. Starting from chiral building blocks with C2 molecular symmetry, the asymmetric unit was determined by MAS NMR spectroscopy, index low-resolution TEM diffraction data, and resolve reflection conditions, and for the first time the ability to determine the space group from reciprocal space data using this hybrid approach was shown. Transfer of molecular C2 symmetry into P2/c packing symmetry provided a connection across length scales to overcome both lack of long-range order and missing diffraction-phase information. Refinement with heteronuclear distance constraints confirmed the racemic P2/c packing that was scaffolded by molecular recognition of salphen zinc in a pseudo-octahedral environment with bromide and with alkyl chains folding along the phenazine. The NDI light-harvesting stacks ran orthogonal to the intermolecular electric dipole moment present in the solid. Finally, the orientation of flexible lamellae on an electrode surface was determined.