Synthesis and light‐emitting properties of platinum‐containing oligoynes and polyynes derived from oligo(fluorenyleneethynylenesilylene)s

A series of blue‐light‐emitting oligo(fluorenyleneethynylenesilylene)s (OFESs) of the general formula HC?CRC?C(EC?CRC?C)_mEC?CRC?CH (E = SiPh₂, SiMe₂, or SiMe₂? SiMe₂; m = 0–2; R = 9,9‐dihexylfluorene‐2,7‐diyl) and their phosphorescent platinum‐containing oligoynes and polyynes were synthesized and characterized. The solution properties and regiochemical structures of this new structural class of organosilicon‐based polyplatinayne polymers {trans‐[? Pt(PBu₃)₂C ?CRC?C(EC?CRC?C)_mEC?CRC?C? ]_n} were studied with IR and NMR (¹H, ¹³C, ²⁹Si, and ³¹P) spectroscopy. The optical absorption and photoluminescence spectra of these metallopolymers were examined and compared with their discrete oligomeric model complexes. Our studies led to a novel approach of using the sp³‐silyl moiety as a conjugation interrupter to limit the effective conjugation length in metal polyynes, which could boost the phosphorescence decay rates essential for light‐energy harvesting from the triplet excited state. The influence of the heavy platinum atom and the group 14 silyl unit possessing different side‐group substituents on the thermal and phosphorescence properties was investigated in detail. We also established the goal of studying the evolution of the lowest singlet and triplet excited states with chain length m of OFESs and the nature of E in these metallopolymers. This work indicated that the phosphorescence emission efficiency harnessed through the heavy‐atom effect of platinum in the main chain did not change very much with oligomer chain length m but generally decreased with the E group in the order SiMe₂ > SiMe₂? SiMe₂ > SiPh₂. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4804–4824, 2006     

Mixed-ligand complex formation of (2,2′,2″-terpyridine)copper(I) and (2,2′2″-terpyridine)copper(II) with some sulfur-containing amino acids

Summary Mixed-ligand complex formation of copper(I) with 2,2,2-terpyridine (terpy) and various biologically significant sulfurcontaining amino acids, L [L = cysteine, penicillamine,N-acetylcysteine andN-acetylpenicillamine] was investigated. WithN-acetylcysteine andN-acetylpenicillamine, copper(I) complexes [Cu(terpy)L]HCl have been isolated and characterised. The amino acid in each case bonds to the copper(I) through the sulfur atom only. These complexes are readily oxidised to the corresponding copper(II) complexes which contain a Cu^II-S(mercaptide) bond as demonstrated by the (S)Cu^II LMCT at 420 nm. The e.p.r. and electronic spectroscopic results are consistent with a distorted octahedral structure. Reactions of copper(I) with terpy and cysteine/ penicillamine in weakly acidic medium produce complexes containing two different copper(II) centres. From a strongly acidic medium, a binary copper(I) terpyridine complex is obtained instead and is shown from i.r. spectral absorptions to contain a protonated pyridyl ring.     

Generalized crichton-like ambiguities

We extend the treatment of two-fold ambiguities in elastic scattering (a) by considering only even or only odd waves, and (b) by allowing non-zero inelasticities. We consider physical applications of these results toππ and toαα scattering.     

Stability analysis of impulsive control systems

This paper studies impulsive control systems. Several stability criteria are established by employing the method of Lyapunov functions. These criteria may be used for impulsive feedback control design. As an application, impulsive control of the Lorenz chaotic system is discussed. Numerical experiments are carried out for the control of the Lorenz system. It is shown that small and frequent impulses need to be used in order to stabilize the Lorenz system.     

Theory of shear magnetostriction in amorphous and crystalline ferromagnetic metals

The theory of shear magnetostriction (SMS) in ferromagnetic metallic systems is formulated in terms of Green functions in real space for a tight binding model. This is general enough to include amorphous (“glassy”) alloys, as well as crystalline materials. It is shown that the SMS coefficient λ_s(E_F) must have at least four zeros as a function of band filling E_F through the d-band, which explains the change in sign between Fe alloys and Co, Ni alloys. A method is presented for computing the indefinite integral of the imaginary part of the product of two Green functions expressed as continued fractions, not necessarily over the same band width, and some preliminary calculations explore the importance of various terms.