Accelerated growth of a molecular-based material that is an active participant in its continuing self-propagated assembly has been demonstrated. This nonlinear growth process involves diffusion of palladium into a network consisting of metal-based chromophores linked via palladium.

The term "frustration" in the context of magnetism was originally used by P. W. Anderson and quickly adopted for application to the description of spin glasses and later to very special lattice types, such as the kagomé. The original use of the term was to describe systems with competing antiferromagnetic interactions and is important in current condensed matter physics in areas such as the description of emergent magnetic monopoles in spin ice. Within molecular magnetism, at least two very different definitions of frustration are used. Here we report the synthesis and characterization of unusual ninemetal rings, using magnetic measurements and inelastic neutron scattering, supported by density functional theory calculations. These compounds show different electronic/magnetic structures caused by frustration, and the findings lead us to propose a classification for frustration within molecular magnets that encompasses and clarifies all previous definitions. ,4,7-triazacyclononane). One area where molecular magnetism might contribute is in spin frustration (3), which is important in condensed matter physics in areas such as spin ice (4) and spin liquids (5). Potential model systems would be odd-numbered metal rings where the metal array forms equilateral triangles, or regular pentagons, heptagons, and larger 2D rings. Alternatively 3D solids made from regular odd-numbered rings should also be frustrated, e.g., regular tetrahedra and octahedra contain triangular faces and regular icosahedra contain pentagonal faces.Studies of spin frustration in molecular systems are largely restricted to that of triangular trimetallic species (6, 7). There are a few reports of five-metal rings but no detailed magnetic studies of such compounds (8), with the exception of a {Cu 5 } cage (9). The only significant examples of larger frustrated molecules are studies of the {M 30 } Keplerates (10) and a recent report of a heptametallic {VO} 7 ring (11), where the studies are limited to low temperature magnetization. There is also a report of an {Fe 9 } complex that can, very approximately, be described as a nine-metal ring (12).A further difficulty is that precisely what is meant by frustration varies in this area. The strictest definition used in molecular magnetism, from Kahn (13), states that frustration must result in a spin degenerate ground state, typically a degenerate pair of S = 1/2 states. Surprisingly, this definition excludes all possible models built from integer spins, as in such cases (for example a regular pentagon of s = 1 spins), the ground total spin state is unique and has S = 0. This definition thus seems prohibitively strict. At the other extreme, the term frustration has been used to describe cases where there are competing antiferromagnetic interactions, even where those interactions result in a unique spin ground state that can be described using a classical picture, with spins represented as arrows pointing alternately up and down. This definition seems, if anything, too permissive.We have reported studies of...

The Rh(II) mononuclear complexes [(PNPtBu)RhCl][BF4] (2), [(PNPtBu)Rh(OC(O)CF3)][OC(O)CF3] (4), and [(PNPtBu)Rh(acetone)][BF4]2 (6) were synthesized by oxidation of the corresponding Rh(I) analogs with silver salts. On the other hand, treatment of (PNPtBu)RhCl with AgOC(O)CF3 led only to chloride abstraction, with no oxidation. 2 and 6 were characterized by X-ray diffraction, EPR, cyclic voltammetry, and dipole moment measurements. 2 and 6 react with NO gas to give the diamagnetic complexes [(PNPtBu)Rh(NO)Cl][BF4] (7) and [(PNPtBu)Rh(NO)(acetone)][BF4]2 (8) respectively. 6 is reduced to Rh(I) in the presence of phosphines, CO, or isonitriles to give the Rh(I) complexes [(PNPtBu)Rh(PR3)][BF4] (11, 12) (R = Et, Ph), [(PNPtBu)Rh(CO)][BF4] (13) and [(PNPtBu)Rh(L)][BF4] (15, 16) (L = tert-butyl isonitrile or 2,6-dimethylphenyl isonitrile), respectively. On the other hand, 2 disproportionates to Rh(I) and Rh(III) complexes in the presence of acetonitrile, isonitriles, or CO. 2 is also reduced by triethylphosphine and water to Rh(I) complexes [(PNPtBu)RhCl] (1) and [(PNPtBu)Rh(PEt3)][BF4] (11). When triphenylphosphine and water are used, the reduced Rh(I) complex reacts with a proton, which is formed in the redox reaction, to give a Rh(III) complex with a coordinated BF4, [(PNPtBu)Rh(Cl)(H)(BF4)] (9).

Four novel mononuclear tetrahedral cobalt(II) complexes containing exocyclic mesoionic ligands of molecular formulae [Co(II)(L1)(X)2(MeCN)] X = Cl (1) or Br (2) and [Co(II)(L2)(X)2(MeCN)], X = Cl (3) or Br (4) have been reported. It is found that simple substitution of L1 (O donor in 1 and 2) by L2 (S donor in 3 and 4) results in switching of the single ion magnetic anisotropy parameter (D) from positive to negative, with a significant change in magnitude.

The copper(II) complex [Cu(dppz)(2)Cl]Cl () has been prepared, structurally characterized and its DNA binding and cleavage properties studied (dppz, dipyridophenazine). Crystal structure of 1xdppzxH(2)O shows the presence of the monocationic copper(II) complex containing two dppz ligands and one chloride in the five coordinate structure. While one bidentate chelating dppz ligand occupies the basal plane, the other dppz ligand shows an axial/equatorial mode of bonding. The chloride ligand binds at the basal plane. The complex crystallizes with dppz and water as lattice molecules. The dppz moieties in the metal-bound and free forms are involved in pi-pi stacking interactions. The one-electron paramagnetic complex shows a visible spectral d-d band at 707 nm in DMF and displays quasireversible cyclic voltammetric response for the Cu(II)/Cu(I) couple near 0.1 V vs. SCE in DMF-0.1 M TBAP. The complex which is an avid binder to calf thymus DNA giving a binding constant (K(b)) value of 2.0 x 10(4) M(-1) in DMF-Tris buffer, cleaves supercoiled pUC19 DNA in an oxidative manner in the presence of mercaptopropionic acid (MPA) as a reducing agent or on photo irradiation at 312 nm. Control experiments show major groove binding and DNA cleavage via the formation of hydroxyl radical in the presence of MPA and by singlet oxygen in the photocleavage reaction. The complex exhibits significant hydrolytic cleavage of DNA in the dark in the absence of any additives at a rate of approximately 3.0 h(-1). The hydrolytic nature of the DNA cleavage is evidenced from the T4 ligase experiments converting the nicked circular form to its original supercoiled form quantitatively. Complex presents a rare example of copper-based major groove directing efficient synthetic hydrolase.

A layer of logic: A series of Boolean operations has been demonstrated with redox‐active monolayers of osmium and ruthenium complexes on glass substrates. High stability, selective reactivity, and reversible redox‐chemistry, coupled with significant optical changes, make these monolayers versatile logic gates. The electron‐transfer‐based systems are suitable as standalone systems or as operational parts in logic circuits.

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Density functional studies have been performed on ten different {Gd(III)-radical} complexes exhibiting both ferro and antiferromagnetic exchange interaction with an aim to assess a suitable exchange-correlation functional within DFT formalism. This study has also been extended to probe the mechanism of magnetic coupling and to develop suitable magneto-structural correlations for this pair. Our method assessments reveal the following order of increasing accuracy for the evaluation of J values compared to experimental coupling constants: B(40HF)LYP < BHandHLYP < TPSSH < PW91 < PBE < BP86 < OLYP < BLYP < PBE0 < X3LYP < B3LYP < B2PLYP. Grimme's double-hybrid functional is found to be superior compared to other functionals tested and this is followed very closely by the conventional hybrid B3LYP functional. At the basis set front, our calculations reveal that the incorporation of relativistic effect is important in these calculations and the relativistically corrected effective core potential (ECP) basis set is found to yield better Js compared to other methods. The supposedly empty 5d/6s/6p orbitals of Gd(III) are found to play an important role in the mechanism of magnetic coupling and different contributions to the exchange terms are probed using Molecular Orbital (MO) and Natural Bond Orbital (NBO) analysis. Magneto-structural correlations for Gd-O distances, Gd-O-N angles and Gd-O-N-C dihedral angles are developed where the bond angles as well as dihedral angle parameters are found to dictate the sign and strength of the magnetic coupling in this series.