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AbstractThe reaction of Re(CO)5Br with deprotonated 1H‐(5‐(2,2′:6′,2′′‐terpyridine)pyrid‐2‐yl)tetrazole yields a triangular assembly formed by tricarbonyl Re(I) vertices. Photophysical measurements reveal blue‐green emission with a maximum at 520 nm, 32 % quantum yield, and 2430 ns long‐lived excited state decay lifetime in deaerated dichloromethane solution. Coordination of lanthanoid ions to the terpyridine units red‐shifts the emission to 570 nm and also reveals efficient (90 %) and fast sensitisation of both Eu(III) and Yb(III) at room temperature, with a similar rate constant kET on the order of 107 s−1. Efficient sensitisation of Eu(III) from Re(I) is unprecedented, especially when considering the close proximity in energy between the donor and acceptor excited states. On the other hand, comparative measurements at 77 K reveal that energy transfer to Yb(III) is two orders of magnitude slower than that to Eu(III). A two‐step mechanism of sensitisation is therefore proposed, whereby the rate‐determining step is a thermally activated energy transfer step between the Re(I) centre and the terpyridine functionality, followed by rapid energy transfer to the respective Ln(III) excited states. At 77 K, the direct Re(I) to Eu(III) energy transfer seems to proceed via a ligand‐mediated superexchange Dexter‐type mechanism. Show less

Zeta potential is commonly referred as surface charge density and is a key factor in modulating the structural and functional properties of nucleic acids. Although the negative charge density of B-DNA is well understood, there is no prior description of the zeta potential measurement of Z-DNA. In this study, for the first time we discover the zeta potential difference between B-DNA and lanthanum chloride-induced Z-DNA. A series of linear repeat i.e. (CG)n and (GC)n DNA as well as branched DNA (bDNA) structures was used for the B-to-Z DNA transition. Herein, the positive zeta potential of Z-DNA has been demonstrated as a powerful tool to discriminate between B-form and Z-form of DNA. The generality of the approach has been validated both in linear and bDNA nanostructures. Thus, we suggest zeta potential can be used as an ideal signature for the left-handed Z-DNA. Show less

AbstractMetal‐driven self‐assembly is one of the most effective approaches to lucidly design a large range of discrete 2D and 3D coordination architectures/complexes. Palladium(II)‐based self‐assembled coordination architectures are usually prepared by using suitable metal components, in either a partially protected form (PdL′) or typical form (Pd; charges are not shown), and designed ligand components. The self‐assembled molecules prepared by using a metal component and only one type of bi‐ or polydentate ligand (L) can be classified in the homoleptic series of complexes. On the other hand, the less explored heteroleptic series of complexes are obtained by using a metal component and at least two different types of non‐chelating bi‐ or polydentate ligands (such as La and Lb). Methods that allow the controlled generation of single, discrete heteroleptic complexes are less understood. A survey of palladium(II)‐based self‐assembled coordination cages that are heteroleptic has been made. This review article illustrates a systematic collection of such architectures and credible justification of their formation, along with reported functional aspects of the complexes. The collected heteroleptic assemblies are classified here into three sections: 1) [(PdL′)m(La)x(Lb)y]‐type complexes, in which the denticity of La and Lb is equal; 2) [(PdL′)m(La)x(Lb)y]‐type complexes, in which the denticity of La and Lb is different; and 3) [Pdm(La)x(Lb)y]‐type complexes, in which the denticity of La and Lb is equal. Representative examples of some important homoleptic architectures are also provided, wherever possible, to set a background for a better understanding of the related heteroleptic versions. The purpose of this review is to pave the way for the construction of several unique heteroleptic coordination assemblies that might exhibit emergent supramolecular functions. Show less

In animals of the same species, the reflexes, having evolved similarly, in a few milliseconds, automatically activate the corresponding reflex arch and without the intervention of the animal generate the adequate response: medullary, mesencephalic or trans-hemispheric. These neurophysiological functions have allowed the animals to be free from predators and increasy their longevity and, as a consequence, the appearance of numerous species during millions of years. A further step in the reflexes evolution, the instincts emerged and their activity, a result of neuro-hormonal functions, stimulates the male's sexual appetite when the females are receptive for their copulation and fecundation. Show less