Beyond Common Metal–Metal Bonds, κ3-Bis(donor)ferrocenyl→Transition-Metal Interactions

Ligands with 1,1′-bis(donor)ferrocene motif are capable of a wide range of binding modes, including the trans chelation mode in which there is a Fe−M interaction (κ³-D,Fe,D), in the form of a dative Fe→TM bond (TM=transition metal). This Minireview will explore the nature of this Fe–TM interaction thorough select examples as well as how to characterize a Fe→TM dative bond using physical, computational, and spectroscopic techniques.     

Ionic Assembly,Anion–π, Magnetic,and Electronic Attributes of Ambient Stable Naphthalenediimide Radical Ions

Organic spin-based molecular materials are considered to be attractive for the generation of functional materials with emergent optoelectronic, magnetic, or magneto-conductive properties. However, the major limitations to the utilization of organic spin-based systems are their high reactivity, instability, and propensity for dimerization. Herein, we report the synthesis, characterization, and magnetic and electronic studies of three ambient stable radical ions ( 1 a^.+ , 1 b^.+ , and 1 c^.+ ). The radical ions 1 b^.+ and 1 c^.+ with BPh₄⁻ and BF₄⁻ counter anions, respectively, were synthesized in excellent yields by means of anion metathesis of 1 a^.+ with Br⁻ as its counter anion. Notably, synthesis of 1 a^.+ was achieved in an ecofriendly, solvent-free protocol. The radical ions were characterized by means of single-crystal X-ray diffraction studies, which revealed the discrete nature of the radical ions and extensive hydrogen-bonding interactions within the radical ions and with the counter anions. Thus, radical ions can be organized to form infinite supramolecular arrays using weak noncovalent interactions. In addition, the Br⁻, BF₄⁻, and BPh₄⁻ anions formed diverse types of anion–π interactions with the naphthalene and imide rings of the radical ions. The radical ions were characterized by means of X-band electron paramagnetic resonance (EPR) spectroscopy in solution and in the solid state. Magnetic studies revealed their paramagnetic nature in the range of 10 to 300 K. The radical ions exhibited high resistivity approaching the gigaohm (GΩ) scale. In addition, the radical ions exhibited panchromism.     

The Hydrogen Bond and Beyond: Perspectives for Rotational Investigations of Non-Covalent Interactions

In the last decade, experiment and theory have expanded our vision of non-covalent interactions (NCIs), shifting the focus from the conventional hydrogen bond to new bridging interactions involving a variety of weak donor/acceptor partners. Whereas most experimental data originate from condensed phases, the introduction of broadband (chirped-pulse) microwave fast-passage techniques has revolutionized the field of rotational spectroscopy, offering unexplored avenues for high-resolution studies in the gas phase. We present an outlook of hot topics for rotational investigations on isolated intermolecular clusters generated in supersonic jet expansions. Rotational spectra offer very detailed structural data, easily discriminating the isomeric or isotopic composition and effectively cancelling any solvent, crystal, or matrix bias. The direct comparison with quantum mechanical predictions provides insight into the origin of the inter- and intramolecular interactions with much greater precision than any other spectroscopic technique, simultaneously serving as test-bed for fine-tuning of theoretical methods. We present recent examples of rotational investigations around three topics: oligomer formation, chiral recognition, and identification of halogen, chalcogen, pnicogen, or tetrel bonds. The selected examples illustrate the benefits of rotational spectroscopy for the structural and energetic assessment of inter-/intramolecular interactions, which may help to move from fundamental research to applications in supramolecular chemistry and crystal engineering.     

Chemistry of Diruthenium and Dirhodium Analogues of Pentaborane(9): Synthesis and Characterization of Metal N,S‐Heterocyclic Carbene and B‐Agostic Complexes

Building upon our earlier results on the synthesis of electron‐precise transition‐metal–boron complexes, we continue to investigate the reactivity of pentaborane(9) and tetraborane(10) analogues of ruthenium and rhodium towards thiazolyl and oxazolyl ligands. Thus, mild thermolysis of nido‐[(Cp*RuH)₂B₃H₇] ( 1 ) with 2‐mercaptobenzothiazole (2‐mbtz) and 2‐mercaptobenzoxazole (2‐mboz) led to the isolation of Cp*‐based (Cp*=η⁵‐C₅Me₅) borate complexes 5 a , b [Cp*RuBH₃L] ( 5 a : L=C₇H₄NS₂; 5 b : L=C₇H₄NOS)) and agostic complexes 7 a , b [Cp*RuBH₂(L)₂], ( 7 a : L=C₇H₄NS₂; 7 b : L=C₇H₄NOS). In a similar fashion, a rhodium analogue of pentaborane(9), nido‐[(Cp*Rh)₂B₃H₇] ( 2 ) yielded rhodaboratrane [Cp*RhBH(L)₂], 10 (L=C₇H₄NS₂). Interestingly, when the reaction was performed with an excess of 2‐mbtz, it led to the formation of the first structurally characterized N,S‐heterocyclic rhodium‐carbene complex [(Cp*Rh)(L₂)(1‐benzothiazol‐2‐ylidene)] ( 11 ) (L=C₇H₄NS₂). Furthermore, to evaluate the scope of this new route, we extended this chemistry towards the diruthenium analogue of tetraborane(10), arachno‐[(Cp*RuCO)₂B₂H₆] ( 3 ), in which the metal center possesses different ancillary ligands.     

Big,Strong, Neutral,Twisted, and Chiral π Acids

General synthetic access to expanded π‐acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion–π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron‐withdrawing substituents decreases and the high π acidity needed for strong anion–π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion–π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from ?3.96 to ?4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X‐ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation–π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches ?4.45 eV, whereas two sulfone moieties give a value of ?4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion–π interactions, these conceptually innovative π‐acidic surfaces are also of interest as electron transporters in conductive materials.     

Regulation of Charge Delocalization in a Heteronuclear Fe2Ru System by a Stepwise Photochromic Process

Heteronuclear complexes FeCp₂?DTE?C?C?Ru(dppe)₂Cl ( 1 o ; dppe=1,2‐bis(diphenylphosphino)ethane, Cp=cyclopentadienyl, DTE=dithienylethene) and FeCp₂?DTE?C?C?Ru(dppe)₂?C?C?DTE?FeCp₂ ( 2 oo ), with redox‐active ferrocenyl and ruthenium centers separated by a photochromic DTE moiety, were prepared to achieve photoswitchable charge delocalization and Fe???Ru electronic communication. Upon UV‐light irradiation of 2 oo , the Fe???Ru heterometallic electronic interaction is increasingly facilitated with stepwise photocyclization, 2 oo → 2 co → 2 cc ; this is ascribed to the gradual increase in π‐conjugated systems. The near‐infrared absorptions in mixed‐valence species [ 2 oo ]⁺/[ 2 co ]⁺/[ 2 cc ]⁺ are gradually intensified following the conversion of [ 2 oo ]⁺→[ 2 co ]⁺→[ 2 cc ]⁺, which demonstrates that the extent of charge delocalization shows progressive enhancement with stepwise photocyclization. As revealed by electrochemical, spectroscopic, and theoretical studies, complex 2 exhibits nine switchable states through stepwise photochromic and reversible redox processes.     

Insights into the Intraspecific Variability of the above and Belowground Emissions of Volatile Organic Compounds in Tomato

The in-vivo monitoring of volatile organic compound (VOC) emissions is a potential non-invasive tool in plant protection, especially in greenhouse cultivation. We studied VOC production from above and belowground organs of the eight parents of the Multi-Parent Advanced Generation Intercross population (MAGIC) tomato population, which exhibits a high genetic variability, in order to obtain more insight into the variability of constitutive VOC emissions from tomato plants under stress-free conditions. Foliage emissions were composed of terpenes, the majority of which were also stored in the leaves. Foliage emissions were very low, partly light-dependent, and differed significantly among genotypes, both in quantity and quality. Soil with roots emitted VOCs at similar, though more variable, rates than foliage. Soil emissions were characterized by terpenes, oxygenated alkanes, and alkenes and phenolic compounds, only a few of which were found in root extracts at low concentrations. Correlation analyses revealed that several VOCs emitted from foliage or soil are jointly regulated and that above and belowground sources are partially interconnected. With respect to VOC monitoring in tomato crops, our results underline that genetic variability, light-dependent de-novo synthesis, and belowground sources are factors to be considered for successful use in crop monitoring.     

Doxorubicin Encapsulation in Carbon Nanotubes Having Haeckelite or Stone–Wales Defects as Drug Carriers: A Molecular Dynamics Approach

Doxorubicin (DOX), a recognized anticancer drug, forms stable associations with carbon nanotubes (CNTs). CNTs when properly functionalized have the ability to anchor directly in cancerous tumors where the release of the drug occurs thanks to the tumor slightly acidic pH. Herein, we study the armchair and zigzag CNTs with Stone–Wales (SW) defects to rank their ability to encapsulate DOX by determining the DOX-CNT binding free energies using the MM/PBSA and MM/GBSA methods implemented in AMBER16. We investigate also the chiral CNTs with haeckelite defects. Each haeckelite defect consists of a pair of square and octagonal rings. The armchair and zigzag CNT with SW defects and chiral nanotubes with haeckelite defects predict DOX-CNT interactions that depend on the length of the nanotube, the number of present defects and nitrogen doping. Chiral nanotubes having two haeckelite defects reveal a clear dependence on the nitrogen content with DOX-CNT interaction forces decreasing in the order 0N > 4N > 8N. These results contribute to a further understanding of drug-nanotube interactions and to the design of new drug delivery systems based on CNTs.     

Study on the Relationship between Emulsion Properties and Interfacial Rheology of Sugar Beet Pectin Modified by Different Enzymes

The contribution of rheological properties and viscoelasticity of the interfacial adsorbed layer to the emulsification mechanism of enzymatic modified sugar beet pectin (SBP) was studied. The component content of each enzymatic modified pectin was lower than that of untreated SBP. Protein and ferulic acid decreased from 5.52% and 1.08% to 0.54% and 0.13%, respectively, resulting in a decrease in thermal stability, apparent viscosity, and molecular weight (Mw). The dynamic interfacial rheological properties showed that the interfacial pressure and modulus (E) decreased significantly with the decrease of functional groups (especially proteins), which also led to the bimodal distribution of particle size. These results indicated that the superior emulsification property of SBP is mainly determined by proteins, followed by ferulic acid, and the existence of other functional groups also promotes the emulsification property of SBP.