Mikhail F. Budyka

Multifunctional Photonic Molecular Logic Gate Based On A Biphotochromic Dyad With Reduced Energy Transfer.

Using molecular logic gates (MLGs) for information processing attracts attention due to perspectives of creating molecular computers. Biphotochromic dyads are suitable models of photonic MLGs. However, they suffer from one weakness: the activity of one of the photochromes is often quenched because of Förster resonance energy transfer (FRET). Herein, we designed a dyad with reduced FRET, in which both photochromes keep their photoactivity thanks to spectral and spatial separation, allowing MLG switching between different states. This novel dyad reproduces the functionality of the full set of 16 two-input gates, as well a reversible gate-dual inverter, all gates are photonic.

Microwave-assisted one-pot synthesis of hybrid nanosystems based on CdS quantum dots functionalized with organic chromophores: effect of the chromophore nature on the nanosystem composition

A novel method of one-pot microwave assisted synthesis was employed to prepare hybrid nanosystems (HNSs) with CdS quantum dots (QD) covered by an organic shell containing capping “background” ligand (benzylmercaptan, BM) and functional ligand (FL) with a styrylquinoline (SQ) or merocyanine (MC) chromophore group. An average amount (n) of the FL molecules in the HNS organic shell was measured. We herein report on an unusual dependence of n on the FL relative concentration in the source solution. A non-linear dependence resembling a cooperative effect is found for the SQ-FL, and a linear dependence with critical concentration is found for the MC-FL. The effects are suggested to be associated with the peculiarities of microwave activation of the ligands, which are built into the organic shell of the HNS as a result of a kinetically rather than thermodynamically controlled process. These data shed light on the problem of the formation of the covering organic shell on the QD surface in different conditions.

EPR studies on branched high-spin arylnitrenes.

The UV (λ>305 nm) photolysis of triazide 3 in 2-methyl-tetrahydrofuran glass at 7 K selectively produces triplet mononitrene 4 (g=2.003, D(T)=0.92 cm(-1), E(T)=0 cm(-1)), quintet dinitrene 6 (g=2.003, D(Q)=0.204 cm(-1), E(Q)=0.035 cm(-1)), and septet trinitrene 8 (g=2.003, D(S)=-0.0904 cm(-1), E(S) =-0.0102 cm(-1)). After 45 min of irradiation, the major products are dinitrene 6 and trinitrene 8 in a ratio of ∼1:2, respectively. These nitrenes are formed as mixtures of rotational isomers each of which has slightly different magnetic parameters D and E. The best agreement between the line-shape spectral simulations and the experimental electron paramagnetic resonance (EPR) spectrum is obtained with the line-broadening parameters Γ(E(Q))=180 MHz for dinitrene 6 and Γ(E(S))=330 MHz for trinitrene 8. According to these line-broadening parameters, the variations of the angles Θ in rotational isomers of 6 and 8 are expected to be about ±1 and ±3°, respectively. Theoretical estimations of the magnetic parameters obtained from PBE/DZ(COSMO)//UB3LYP/6-311+G(d,p) calculations overestimate the E and D values by 1 and 8 %, respectively. Despite the large distances between the nitrene units and the extended π systems, the zero field splitting (zfs) parameters D are found to be close to those in quintet dinitrenes and septet trinitrenes, where the nitrene centers are attached to the same aryl ring. The large D values of branched septet nitrenes are due to strong negative one-center spin-spin interactions in combination with weak positive two-center spin-spin interactions, as predicted by theoretical considerations.

Synthesis and properties of heterocyclic analogs of 4-azidochalcone

A study has been made of the spectral and photochemical properties of a series of heterocyclic analogs of 4-azidochalcone, specifically the pyridine, quinoline, isoquinoline, and quinoxaline derivatives. It has been shown that the absorption spectra of most of the 4-azidocinnamoylarenes are shifted bathochromically in comparison with 4-azidochalcone. The quantum yields of photodissociation of the compounds that were investigated were found to vary within the limits 0.70±0.15. With steric hindrance for the planar conformation of the molecule, a hypsochromic shift of the absorption spectra is observed, along with a slight decrease of the quantum yield.