Preferred orientation in an angled intercalation site of a chloro-substituted lambda- [Ru(TAP)2(dppz)]2+ complex bound to d(TCGGCGCCGA)2

The crystal structure of the ruthenium DNA ‘light-switch’ complex -[Ru(TAP)2(11-Cl-dppz)]2+ (TAP = tetraazaphenanthrene, dppz = dipyrido[3,2-a':2',3'-c]phenazine)) bound to the oligonucleotide duplex d(TCGGCGCCGA)2 is reported. The synthesis of the racemic ruthenium complex is described for the first time, and the racemate was used in this study. The crystal structure, at atomic resolution (1.0 Å), shows one ligand as a wedge in the minor groove, resulting in the 51 kinking of the double helix, as with the parent lambda-[Ru(TAP)2(dppz)]2+. Each complex binds to one duplex by intercalation of the dppz ligand and also by semi-intercalation of one of the orthogonal TAP ligands into a second symmetrically equivalent duplex. The 11-Cl substituent binds with the major component (66%) oriented with the 11-chloro substituent on the purine side of the terminal step of the duplex

η3-Allyl carbonyl complexes of group 6 metals: structural aspects, isomerism, dynamic behaviour and reactivity

Transition metal complexes with π-allylic ligands remain an attractive topic in organometallic chemistry, given the numerousreports of a wide variety of synthetic routes, dynamic behaviour and reactivity, structural (including isomerism),spectroscopic and redox properties, and applications in organic synthesis and catalysis. Surprisingly, despite the considerableinterest in the rich and varied chemistry of this family of organometallic compounds, there is no recent review. This review is focused on π-allylic representatives of low-cost Group-6 metals bearing one or more carbonyl ligand, the coordination sphere being complemented with η5-cyclopentadienyl (Section 2), chelating ligands, including redox-active α-diimines and various complementary diphosphines (Section 3), and novel anionic amidinate or pyrazolate ligands (Section 4). In Section 1, particular attention is paid to rearrangements of the π-allylic ligand, namely exo and endo isomerism, interconversion mechanisms, fluxionality, and agostic interactions. In addition, the application of multinuclear NMR spectroscopy to the elucidation of such isomerism, and the effect of the metal-centre oxidation state on the bonding, dynamic behaviour and reactivity of the π-allylic ligand are described. The detailed mechanistic description of the synthetic routes and dynamic behaviour of selected representatives of α-diimine complexes in Section 2 is followed by a description of the [M(CO)2(η3-allyl-H,R)(α-diimine)]0/+ fragment as a convenient scaffold for diverse monodentate ligands participating in a range of substitution, insertion, intramolecular migration and C–C coupling reactions – frequently involving also the π-allylic ligand, such as allylic alkylation. Special attention is devoted to selected examples of redox and acid-base reactivity of the α-diimine complexes with emphasis on prospects in electrocatalysis. The amidinate (and related pyrazolate) ligands treated in Section 4 may directly replace the π-allylic ligand in some cyclopentadienyl complexes (Section 2) or the α-diimine ligand in some dicarbonyl π-allylic complexes (Section 3). The brief description of their synthetic routes is complemented by intriguing examples of fluxionality and characteristic reactivity encountered for these unusual four-electron donor ligands

The structural effect of Methyl substitution on the binding of Polypyridyl Ru-dppz Complexes to DNA

ABSTRACT: Polypyridyl ruthenium complexes have been intensively studied and possess photophysical properties which are both interesting and useful. They can act as probes for DNA, with a substantial enhancement in emission when bound, and can induce DNA damage upon photoirradiation and therefore, the synthesis and characterization of DNA binding of new complexes is an area of intense research activity. Whilst knowledge of how the binding of derivatives compares to the parent compound is highly desirable, this information can be difficult to obtain. Here we report the synthesis of three new methylated complexes, [Ru(TAP)2(dppz-10-Me).2Cl, [Ru(TAP)2(dppz-10,12-Me2)].2Cl and [Ru(TAP)2(dppz-11-Me)].2Cl, and examine the consequences for DNA binding through the use of atomic resolution X-ray crystallography. We find that the methyl groups are located in discrete positions with a complete directional preference. This may help to explain the quenching behavior which is found in solution for analogous [Ru(phen)2(dppz)]2+ derivatives

Conformational modulation of sequence recognition in synthetic macromolecules

The different triplet sequences in high molecular weight aromatic copolyimides comprising pyromellitimide units ("I") flanked by either ether-ketone ("K") or ether-sulfone residues ("S") show different binding strengths for pyrene-based tweezer-molecules. Such molecules bind primarily to the diimide unit through complementary π-π-stacking and hydrogen bonding. However, as shown by the magnitudes of 1H NMR complexation shifts and tweezer-polymer binding constants, the triplet "SIS" binds tweezer-molecules more strongly than "KIS" which in turn bind such molecules more strongly than "KIK". Computational models for tweezer-polymer binding, together with single-crystal X-ray analyses of tweezer-complexes with macrocyclic ether-imides, reveal that the variations in binding strength between the different triplet sequences arise from the different conformational preferences of aromatic rings at diarylketone and diarylsulfone linkages. These preferences determine whether or not chain-folding and secondary π−π-stacking occurs between the arms of the tweezermolecule and the 4,4'-biphenylene units which flank the central diimide residue

Design Catalogs: A Systematic Approach to Design and Value Flexibility in Engineering Systems

This paper proposes design catalogs as an efficient systematic process for identifying and evaluating improved designs in engineering systems by exploiting ideas of flexibility. Standard design and evaluation approaches typically do not cope well with a range of possible operating conditions. They often simplify considerations of uncertainty, which may lead to designs that do not perform as well as those responding dynamically to changing conditions. The proposed process addresses the complexity of the design problem under uncertainty, recognizing that it is impossible to analyze all possible combinations of evolutions, and the flexible ways in which the system could adapt over time. The process creates a small subset of designs that collectively perform well over a range of scenarios. It bundles representative scenarios and their flexible responses to enable a more thorough analysis that accounts explicitly for uncertainty—and enable considerations of improved designs. Each element consists of combinations of design variables, parameters, and management decision rules carefully selected, and referred as operating plans. In the example analysis, the process improves economic performance by 37% as compared to standard methods in an infrastructure system case study, while exploring only 3% of the design space. It reaches 86% of the stochastically optimal solution while being 183 times faster computationally in the example numerical study. The systematic property aims for practical applications in industry. In each phase, it gives the freedom to rely on the designer's expertise with the system, or to consider analytical tools already in use at the design organization.National University of Singapore (MOE AcRF Tier 1 Grant WBS R-266-000-061-133)Massachusetts Institute of Technology. Engineering Systems DivisionMassachusetts Institute of Technology. Center for Real Estat

Design Catalogs: A Practical Real Options Valuation Tool for Real Estate Design and Development Planning

IRES Working Paper Serie

SiNx:Tb3+--Yb3+, an efficient down-conversion layer compatible with a silicon solar cell process

SiN x : Tb 3+-Yb 3+, an efficient down-conversion layer compatible with silicon solar cell process Abstract Tb 3+-Yb 3+ co-doped SiN x down-conversion layers compatible with silicon Photovoltaic Technology were prepared by reactive magnetron co-sputtering. Efficient sensitization of Tb 3+ ions through a SiN x host matrix and cooperative energy transfer between Tb 3+ and Yb 3+ ions were evidenced as driving mechanisms of the down-conversion process. In this paper, the film composition and microstructure are investigated alongside their optical properties, with the aim of maximizing the rare earth ions incorporation and emission efficiency. An optimized layer achieving the highest Yb 3+ emission intensity was obtained by reactive magnetron co-sputtering in a nitride rich atmosphere for 1.2 W/cm${}^2$ and 0.15 W/cm${}^2$ power density applied on the Tb and Yb targets, respectively. It was determined that depositing at 200 {\textdegree}C and annealing at 850 {\textdegree}C leads to comparable Yb 3+ emission intensity than depositing at 500 {\textdegree}C and annealing at 600 {\textdegree}C, which is promising for applications toward silicon solar cells.Comment: Solar Energy Materials and Solar Cells, Elsevier, 201