Controlling the Size of Molecular Copper Clusters Supported by a Multinucleating Macrocycle.

The use of a nonrigid, pyridyldialdimine-derived macrocyclic ligand (PDAI) enabled the synthesis of well-defined mono-, di-, tri-, and tetra-nuclear Cu(I) complexes in good yields through rational synthetic means. Starting from mono- and diargentous PDAI complexes, transmetalation to Cu(I) proceeded smoothly with formation of AgX (X = Cl, I) salts to generate mono-, di-, and trinuclear copper complexes. Monodentate supporting ligands (MeCN, xylNC, PMe, PPh) were found to either transmetallate with or bind various di- and trinuclear clusters.

Motor cognition in plants: from thought to real experiments.

Motor cognition involves the process of planning and executing goal-directed movements and recognizing, anticipating, and interpreting others' actions. Motor cognitive functions are generally associated with the presence of a brain and are ascribed only to humans and other animal species. A growing body of evidence suggests that aneural organisms, like climbing plants, exhibit behaviors driven by the intention to achieve goals, challenging our understanding of cognition.

Ascent and Attachment in Pea Plants: A Matter of Iteration.

Pea plants ( L.) can perceive the presence of potential supports in the environment and flexibly adapt their behavior to clasp them. How pea plants control and perfect this behavior during growth remains unexplored.

intertwining as evidence of joint actions in pea plants.

In life, it is common for almost every kind of organism to interact with one another. In the human realm, such interactions are at the basis of joint actions, when two or more agents syntonize their actions to achieve a common goal. Shared intentionality is the theoretical construct referring to the suite of abilities that enable such coordinated and collaborative interactions.

Evidence of motor intentions in plants: A kinematical study.

"How" an action is performed is not solely determined by biomechanical constraints, but it depends on the agent's intention, that is, "why" the action is performed. Recent findings suggest that intentions can be specified at a tangible and quantifiable level in the kinematics of movements; that is, different motor intentions translate into different kinematic patterns. In the present study, we used 3D kinematical analysis to investigate whether the organization of climbing plants' approach-to-grasp action is sensitive to the kind of intention driving their movement toward potential support, namely individual or social.

Decision-Making Underlying Support-Searching in Pea Plants.

Finding a suitable support is a key process in the life history of climbing plants. Those that find a suitable support have greater performance and fitness than those that remain prostrate. Numerous studies on climbing plant behavior have elucidated the mechanistic details of support-searching and attachment.

Classifying Circumnutation in Pea Plants via Supervised Machine Learning.

Climbing plants require an external support to grow vertically and enhance light acquisition. Climbers that find a suitable support demonstrate greater performance and fitness than those that remain prostrate. Support search is characterized by oscillatory movements (i.

Kinematic Evidence of Root-to-Shoot Signaling for the Coding of Support Thickness in Pea Plants.

Plants such as climbers characterized by stems or tendrils need to find a potential support (e.g., pole, stick, other plants or trees) to reach greater light exposure.

Cracking the code: a comparative approach to plant communication.

The linguistic behavior of humans is usually considered the point of reference for studying the origin and evolution of language. As commonly defined, language is a form of communication between human beings; many have argued that it is unique to humans as there is no apparent equivalent for it in non-human organisms. How language is used as a means of communication is examined in this essay from a biological perspective positing that it is effectively and meaningfully used by non-human organisms and, more specifically, by plants.

The coding of object thickness in plants: When roots matter.

Tendrils are clasping structures used by climbing plants to anchor and support their vines that coil around suitable hosts to achieve the greatest exposure to sunlight. Although recent evidence suggests that climbing plants are able to sense the presence of a potential stimulus in the environment and to plan the tendrils' movements depending on properties such as its thickness, the mechanisms underlying thickness sensing in climbing plants have yet to be uncovered. The current research set out to use three-dimensional kinematical analysis to investigate if and in what way the root system contributed to thickness sensing.

Sowing the seeds of intentionality: Motor intentions in plants.

Motor intention/intentionality has been investigated from a wide variety of perspectives: some researchers have, for example, been focusing on the purely physical and mechanical aspects underlying the control of action, while others have been concentrating on subjective intentionality. Basically, all approaches ranging from the neuroscientific to phenomenological-inspired ones have been used to investigate motor intentions. The current study set out to examine motor intentions in connection to plant behavior utilizing the final goal of plant action as the definition of its motor intention.

Can Plants Move Like Animals? A Three-Dimensional Stereovision Analysis of Movement in Plants.

In this article we adapt a methodology customarily used to investigate movement in animals to study the movement of plants. The targeted movement is circumnutation, a helical organ movement widespread among plants. It is variable due to a different magnitude of the trajectory (amplitude) exhibited by the organ tip, duration of one cycle (period), circular, elliptical, pendulum-like or irregular shape and the clockwise and counterclockwise direction of rotation.

Pyridyldiimine macrocyclic ligands: Influences of template ion, linker length and imine substitution on ligand synthesis, structure and redox properties.

A series of 2,6-diiminopyridine-derived macrocyclic ligands have been synthesized via [2+2] condensation around alkaline earth metal triflate salts. The inclusion of a -butyl group at the 4-position of the pyridine ring of the macrocyclic synthons results in macrocyclic complexes that are soluble in common organic solvents, thereby enabling a systematic comparison of the physical properties of the complexes by NMR spectroscopy, mass spectrometry, solution-phase UV-Vis spectroscopy, cyclic voltammetry and single-crystal X-ray crystallography. Solid-state structures determined crystallographically demonstrate increased twisting in the ligand, concurrent with either a decrease in ion size or an increase in macrocycle ring size (18, 20, or 22 membered rings).

Tuning metal-metal interactions for cooperative small molecule activation.

Cluster complexes have attracted interest for decades due to their promise of drawing analogies to metallic surfaces and metalloenzyme active sites, but only recently have chemists started to develop ligand scaffolds that are specifically designed to support multinuclear transition metal cores. Such ligands not only hold multiple metal centers in close proximity but also allow for fine-tuning of their electronic structures and surrounding steric environments. This Feature Article highlights ligand designs that allow for cooperative small molecule activation at cluster complexes, with a particular focus on complexes that contain metal-metal bonds.

N-H Bond Formation at a Diiron Bridging Nitride.

Despite their connection to ammonia synthesis, little is known about the ability of iron-bound, bridging nitrides to form N-H bonds. Herein we report a linear diiron bridging nitride complex supported by a redox-active macrocycle. The unique ability of the ligand scaffold to adapt to the geometric preference of the bridging species was found to facilitate the formation of N-H bonds via proton-coupled electron transfer to generate a μ-amide product.

Interdependent Metal-Metal Bonding and Ligand Redox-Activity in a Series of Dinuclear Macrocyclic Complexes of Iron, Cobalt, and Nickel.

This report describes an isostructural series of dinuclear iron, cobalt, and nickel complexes bound by a redox-active macrocyclic ligand. The series spans five redox levels (34-38 e/cluster core), allowing for a detailed investigation into both the degree of metal-metal interaction and the extent of ligand-based redox-activity. Magnetometry, electrochemistry, UV-vis-NIR absorption spectroscopy, and crystallography were used in conjunction with DFT computational analyses to extract the electronic structures of the six homodinuclear complexes.

Tuning Metal-Metal Interactions through Reversible Ligand Folding in a Series of Dinuclear Iron Complexes.

A dinucleating macrocyclic ligand with two redox-active, pyridyldiimine components was shown to undergo reversible ligand folding to accommodate various substitution patterns, metal ion spin states, and degrees of Fe-Fe bonding within the cluster. An unfolded-ligand geometry with a rectangular Fe(μ-Cl) core and an Fe-Fe distance of 3.3262(5) Å served as a direct precursor to two different folded-ligand complexes.

Ring-Size-Modulated Reactivity of Putative Dicobalt-Bridging Nitrides: C-H Activation versus Phosphinimide Formation.

Dicobalt complexes supported by flexible macrocyclic ligands were used to target the generation of the bridging nitrido species [( PDI )Co (μ-N)(PMe ) ] (PDI=2,6-pyridyldiimine; n=2, 3, corresponding to the number of catenated methylene units between imino nitrogen atoms). Depending on the size of the macrocycle and the reaction conditions (solution versus solid-state), the thermolysis of azide precursors yielded bridging phosphinimido [( PDI )Co (μ-NPMe )(PMe ) ] , amido [( PDI )Co (μ-NH )(PMe ) ] (n=2, 3), and C-H amination [( PDI *-μ-NH)Co (PMe ) ] products. All results are consistent with the initial formation of [( PDI )Co (μ-N)(PMe ) ] , followed by 1) PMe attack on the nitride, 2) net hydrogen-atom transfer to form N-H bonds, or 3) C-H amination of the alkyl linker of the PDI ligand.

Synthesis, Structure, Multiband Optical, and Electrical Conductive Properties of a 3D Open Cubic Framework Based on [Cu8Sn6S24](z-) Clusters.

Two compounds with the formulas of Na4Cu32Sn12S48·4H2O and K11Cu32Sn12S48·4H2O were synthesized via flux (with thiourea as reactive flux) and hydrothermal method, respectively. The black crystals of Na4Cu32Sn12S48·4H2O and K11Cu32Sn12S48·4H2O both crystallize in the cubic space group of Fm3̅c with the cell constants a = 17.921(2) Å and a = 18.