English

Inorg. Chem., 2016, 55, 4720-4732

Статья пользователей РЦ МРМИ, попавшая на обложку журнала Inorganic Chemistry:

A.A. Penney, V.V. Sizov, E.V. Grachova, D.V. Krupenya, V.V. Gurzhiy, G.L. Starova, S.P. Tunik

“Aurophilicity in Action: Fine-Tuning the Gold(I)–Gold(I) Distance in the Excited State To Modulate the Emission in a Series of Dinuclear Homoleptic Gold(I)–NHC Complexes”

Inorg. Chem., 2016, 55, 4720-4732
DOI:10.1021/acs.inorgchem.5b02722

The formation of exciplexes between cationic dinuclear Au(I) bis(carbene) complexes and bromide ions was found to decrease the Au−Au distance in the triplet excited state, leading to pronounced changes in emission. The stimuli-responsive nature of the intracationic aurophilic interaction paves the way for fine-tuning the emission energy and opens new possibilities for practical applications.

Изменения кадрового состава


Из РЦ МРМИ уволилась Эльвира Жиглей. Мы желаем нашему коллеге удачи на новом рабочем месте!

Конгресс Университета Арктики

кадры после трансляции

В рамках Конгресса Университета Арктики (12-16.09.2016, Санкт-Петербург; http://www.uarctic.spbu.ru/) П.М. Толстой выступил с докладом о работе Научного парка СПбГУ на примере РЦ «Магнитно-резонансные методы исследования». Был организован телемост с ресурсным центром, во время которого специалисты А.С. Мазур и М.А. Вовк отвечали на вопросы о текущей работе и выполняемых проектах.

Изменения кадрового состава


Мы рады приветствовать в наших рядах нового сотрудника, Романа Белых. Деятельность Романа направлена на расширение возможностей ЯМР/ЯКР спектрометра Tecmag Redstone.

Synthesis, 2016, 48, 2851-2862

M.S. Mishina, A.Yu. Ivanov, P.S. Lobanov, D.V. Dar’in

“A New Synthesis of 2-Aminoindoles and 6-Aminopyrrolo[3,2-d]pyrimidines from π-Deficient 1,2-Dihaloarenes and Geminal Enediamines”

Synthesis, 2016, 48, 2851-2862
DOI:10.1055/s-0035-1561645

источник: https://www.thieme-connect.de/products/ejournals/abstract/10.1055/s-0035-1561645

An efficient approach for the synthesis of fused 2-aminopyrroles via geminal enediamines and π-deficient 1,2-dihaloarenes is presented. The two-step methodology includes aromatic nucleophilic substitution of the activated halogen of dihaloarene with enediamine C-nucleophilic center followed by Cu-catalyzed intramolecular N-arylation. This approach allows access to a variety of 2-amino-6-nitroindoles and 6-aminopyrrolo[3,2-d]pyrimidines (including N-mono- and N,N-disubstituted) in moderate and good yields under mild conditions.

Cryst. Growth Des., 2016, 16, 2979-2987

E.S. Yandanova, D.M. Ivanov, M.L. Kuznetsov, A.G. Starikov, G.L. Starova, V.Yu. Kukushkin

“Recognition of S···Cl Chalcogen Bonding in Metal-Bound Alkylthiocyanates”

Cryst. Growth Des., 2016, 16, 2979-2987
DOI:10.1021/acs.cgd.6b00346

источник: http://pubs.acs.org/doi/abs/10.1021/acs.cgd.6b00346

Reaction of K2[PtCl4] with excess AlkSCN in water gives the alkylthiocyanate complexes trans-[PtCl2(AlkSCN)2] (Alk = Et 1, nPr 2; 80–85%). These species were studied, in particular, by X-ray crystallography. In the solid state, both 1 and 2 exhibit the previously unreported S···Cl chalcogen bonding, which consolidates the complexes into networks and leads to layered structures. Theoretical density functional theory calculations and Bader’s atoms in molecules analysis demonstrated two types of intermolecular interactions in tetramer (1)4, viz. the S···Cl chalcogen and the H···Cl hydrogen bonds. Despite that each particular S···Cl or H···Cl bonding is weak with the estimated energy of 1–2 kcal/mol, altogether they play a crucial role in the stabilization of the S2Cl2 fragment in (1)4, the basis set of superposition error corrected interaction energy being −12.8 kcal/mol per monomer complex molecule. The chalcogen bonding and the rhomboidal structure of the S2Cl2 fragment can be interpreted in terms of electrostatic arguments as a result of the interaction between the belt of negative electrostatic potential around the Cl atoms and the sulfur σ-holes. The natural bond orbital analysis revealed that both LP(S) → LP*(Pt)/σ*(Pt–N)/σ*(Pt–Cl) and LP(Cl) → σ*(S–C) types of hyperconjugative charge transfers are important in the chalcogen bonding.

Август

В августе выполнено 1059 заявок на сервисные измерения.

Измерено:

  • 1006 спектров 1H
  • 192 спектра 13C
  • 79 спектров DEPT
  • 17 спектров COSY
  • 9 спектров NOESY
  • 2 спектра 31Р
  • 10 спектров 19F

Выполнено 129 заявок на исследовательскую работу.

Chem. Commun., 2016, 52, 5565

D.M. Ivanov, A.S. Novikov, I.V. Ananyev, Y.V. Kirina, V.Yu. Kukushkin

“Halogen bonding between metal centers and halocarbons”

Chem. Commun., 2016, 52, 5565
DOI:10.1039/c6cc01107a

источник: http://pubs.rsc.org/en/Content/ArticleLanding/2016/CC/C6CC01107A#!divAbstract

Metal-involving halogen bonding was detected in a series of associates of CHI3 with trans-[PtX2(NCNAlk2)2] (X = Cl, Br). The HI2C–I⋯η1(Pt) halogen bonding and the bifurcated HI2C–I⋯η2(Pt–Cl) halogen bonding – the latter undergoes the thermally induced reversible HI2C–I⋯η2(Pt–Cl) ⇄ HI2C–I⋯η1(Pt) transformation – were observed and confirmed theoretically.

Статья с обложки

Статья пользователей РЦ МРМИ, попавшая на обложку журнала Eur. J. Inorg. Chem.:

D.M. Ivanov, P.V. Gushchin, A.S. Novikov, M.S. Avdontceva, A.A. Zolotarev, G.L. Starova, Y.-T. Chen, S.-H. Liu, P.-T. Chou, V.Yu. Kukushkin

“Platinum(II)-Mediated Double Coupling of 2,3-Diphenylmaleimidine with Nitrile Functionalities To Give Annulated Pentaazanonatetraenate (PANT) Systems”

Eur. J. Inorg. Chem., 2016, 1480–1487
DOI:10.1002/ejic.201501398

CoverArt

Treatment of trans-[PtCl2(NCR)2] [R = Et 1, nPr 2, tBu 3, CH2Ph 4, Ph 5, p-CF3C6H4 6, NMe2 7, NEt2 8, N(CH2)5 9] with 2.5 equiv. of 2,3-diphenylmaleimidine in CH2Cl2 at room temperature for 5 min [for R = p-CF3C6H4 6, NMe2 7, NEt2 8, N(CH2)5 9] or 14 h (for R = Et 1, nPr 2, tBu 3, CH2Ph 4, Ph 5) furnishes (1,3,5,7,9-pentaazanona-1,3,6,8-tetraenato) platinum(II) [(PANT)PtII; PtCl{HN=C(R)N=CN[C(Ph)=C(Ph)]C=NC(R)=NH}] complexes 10–18. These species are formed by platinum(II)-mediated double coupling of 2,3-diphenylmaleimidine with both nitrile ligands. The formulation of the complexes was supported by satisfactory C, H, and N elemental analyses, which were in agreement with HRESI-MS, IR, and 1H and 13C{1H} NMR spectra. The structures of 10, 11·1/8nC6H14, 15, 16·CCl4, and 17·CHCl3 were determined by single-crystal X-ray diffraction. Absorption and emission studies were performed on representative complexes 10, 15, and 18, and the results show weak phosphorescence maxima at around 730–750 and 770–820 nm in CH2Cl2 and in the solid state, respectively. Further insight into the photophysical properties was gained by time-dependent density functional theory (TD–DFT) with detailed analysis of the corresponding frontier molecular orbitals for the lower-lying transition. The calculated energies of the T1 state (in terms of wavelength) are 715.8 nm for 10, 764.6 nm for 15, and 697.7 nm for 18, and these values are in good agreement with the trend of the first vibronic peaks of their phosphorescence spectra.

Journal of Power Sources, 2016, 304, 102-110

M.A. Smirnov, M.P. Sokolova, N.V. Bobrova, I.A. Kasatkin, E. Lahderanta, G.K. Elyashevich

“Capacitance properties and structure of electroconducting hydrogels based on copoly(aniline e p-phenylenediamine) and polyacrylamide”

Journal of Power Sources, 2016, 304, 102-110
DOI:10.1016/j.jpowsour.2015.11.035

источник: http://www.sciencedirect.com/science/article/pii/S0378775315305334

Electroconducting hydrogels (EH) based on copoly(aniline — p-phenylenediamine) grafted to the polyacrylamide for the application as pseudo-supercapacitor’s electrodes have been prepared. The influence of preparation conditions on the structure and capacitance properties of the systems were investigated: we determined the optimal amount of p-phenylenediamine to obtain the network of swollen interconnected nanofibrils inside the hydrogel which provides the formation of continuous conducting phase. Structure and morphology of the prepared samples were investigated with UVeVIS spectroscopy, scanning electron microscopy (SEM) and wide-angle X-ray diffraction (WAXD). The maximal value of capacitance was 364 F g-1 at 0.2 A g-1. It was shown that the EH samples demonstrate the retention of 50% of their capacity at high current density 16 A g-1. Cycle-life measurements show evidence that capacitance of EH electrodes after 1000 cycles is higher than its initial value for all prepared samples. Changes of the copolymer structure during swelling in water have been studied with WAXD.