Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by ¹H and ¹³C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004     

Design and synthesis of Ru(II-bipyridyl-containing conjugated polymers

A series of novel π-conjugated polymers containing ruthenium bipyridine complexes was synthesized by a cross-coupling reaction and characterized. These polymers exhibit absorption maxima around 330–350 nm (π-π*) and 460–500 nm metal-to-ligand charge transfer (MLCT), respectively. They are soluble in common organic solvents, and all polymers can be converted into transparent films. We investigated the influence of different donating and acceptor diethynylarenes of the ultraviolet-visible spectra. The oxidation potential, which was measured by cyclic- and square-wave voltametry, showed a typical Ru^2+/3+ exhibited at 1.25 V versus the saturated calomel electrode. The polymers were further characterized with photoluminescence measurements. When excited at 442 nm ( 11a ), the polymer exhibited an emission peak at 690 nm. This peak was attributed to the MLCT states. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 722–732, 2004     

Resonance method for IR sensing

A highly sensitive method for infrared radiation detection based on thermal resonance in an active bolometer is set forth. An active bolometer is a self-oscillating system consisting of an IR-sensitive cell in a feedback circuit of an adjustable proportional controller. The analysis of an active bolometer autonomous (dark) dynamics reveals that with a generalized gain factor A variation the system evolves from relaxation type towards oscillating and self-oscillating type. When A=A_c, where A_c is a critical value of the generalized gain factor A, the steady state loses stability through self-excited thermal oscillations. The resonance in a system weakly perturbed by IR radiation modulated at self-oscillation frequency q₀[1+exp(iω_ct)] is considered. It is shown that in a small precritical vicinity =(A−A_c)/A_c of the gain factor the amplitude of forced thermal oscillations is proportional to q₀/A_c. The D^* calculation reveals that the detection power of a passive (A=0) bolometer increases with feedback introduction by a factor of 1/||. The detection powers of feasible versions of an active bolometer are compared.     

Polygermoxanes suitable for biochemical purposes. Part I. Digermoxanes (low-viscosity oils)

In order to replace silicones in some of their biomedical applications, e.g. syringe lubrication, implants ets., a series of digermoxanes (R¹R²R³Ge)₂O (R = n–alkyl, aryl) were synthesized. These compounds are thermally stable oils; their viscosities, depending on the nature of substituents, lie in the range 1–72 cPo (mPa s) at 20°C.     

Synthesis of heteroaryl substituted α‐mercapto acids from thiomalic acid using hexafluoroacetone as protecting and activating reagent

The synthesis of heterocyclic α‐mercapto acids starting from (RS)‐thiomalic acid using hexafluoroacetone as protecting and activating agent is described. The new compounds are useful building blocks for peptide and depsipeptide modification as well as for drug design.     

Surface bodies and p-affine surface area

The surface body is a generalization of the floating body. Its relation to p-affine surface area is studied.