SCIENTIFIC ABSTRACT SHIGORIN, D.N. - SHIGORIN, D.N.

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• Sequence Number: 18
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

5(2,4) SOV/20-125-3-27/63
AUTHORS: Rodionov,A. N., Vasillyeva, V. N., Talalayeva, T. V., Shigorin,
-R.-N., Gurlyanova, Ye. N., Kocheshkov, K. A., Correspon n-g
Member, AS USSR
TITLE. Intermolecular Lithium Bond, Its Influence Upon the Vibration
Spectra of Molecules and Upon the Dipole Moments
(Mezhmolekulyarnaya litiyevaya svyazl, yeye v1iyaniye na
kolebatellnyye spektry molekul i dipolnyye momenty)
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 125, Nr 3, PP 562-565
(USSR)
ABSTRACT: In an earlier paper (Ref 1) the authors proved the formation of
-9 +S -E -;-S
a bond referred to in the title -CH 2- Li ... CH 2- Li (I) and
R-O-Li ... O-Li (II). The lithium bond like the hydrogen bond is
a secondary chemical bond (Ref 2). Type (I) was closely in-
ve8tigated on the basis of infrared absorption spectra. In the
work under review, infrared spectra of Alk-Li compounds with a
varying length of the radical chain were solved in hexane and
Card 1/3 investigated at various concentrations. The ailm was to clarify

SOV/20-125-3-27/63
Intermolecular Lithium Bond, Its Influence Upon the Vibration Spectra of Mole-
cules and Upon the Dipole Moments
the dependence of the intermolecular space, of the stability of
the lithium bond and also of the magnitude of the frequency
displacement of the groups C-Li on the length and on the struc-
ture of the carbon radical. Table 1 as well as figures I and 2
illustrate the results obtained. As may be observed therefrom,
the value of the displacement of the said groups actually de-
creases with increasing chain length. Thus also the stability of
the lithium bond in the complexes decreases. The investigation
of the solutions of ethyl, n-butyl, and n-amyl lithiam in hexane
showed a linear course of the dependence of the dielectricity
constant on the concentration in the case of lower concentra-
tions. This course diverges from the straight line on an in-
crease of concentration (0-4-3-0 mole %). The dipole moment of
ethyl lithium in benzene remains constant between 0.08-0-43mols%
and amounts to 0-87 D. The variation of the dipole moment in
the complex, connected with the formation of lithium, goes
back on the whole to the action of this bond upon the type of
orientation of the dipoles with respect to one another. There@
Card 2/3 fore, the formation of cyclic complexes and especially the type

SOV/20-125-3-27/63
Intermolecular Lithium Bond, Its Influence Upon the Vibration Spectra of Mole-
cules and Upon the Dipole Moments
of the "quadrupoles" must decrease the dipole moment. This ap-
parently takes place in the ethyl lithium solutions in benzene.
It follows from the above that alkyl lithium molecules are as-
sociated both in benzene and in hexane solutions. The character
of the associate depends both on the nature of the solvent and
on the radical composition. The lithium bond considerably in-
fluences the frequency variations of the vibrations of the
C-Li groups and also the dipole moments of the complexes; these
variations here depend on the radical length, on the concentra-
tion of the solutions, and also on the nature of the solvent.
There are 2 figures, 1 table, and 3 references, 2 of which are
Soviet.
ASSOCIATION: Nauchno-issledovatellskiy fiziko-khimicheskiy institut im.
L. Ya. Karpova (Scientific Physico-chemical Research institute
imeni L. Ya. Karpov)
SUBMITTED: December 29, 1958
Card 3/3

5 (2,3,4)
AUTHORS:
TITLE:
PERIODICAL:
ABSTRACT
Card 1/4
Rodionov, A. N., Talalayeva, T. V., SOV/20-1 28--4-26/65
Shigorin, D. N., Kocheshkov, K. A.,
b-oYT'Vffrd*dd1'ag@--Member AS USSR
The Infrared Spectra and Structure of Aromatic Organolithium
Compounds
Doklady Akademii nauk SSSR, 1959, Vol 128, Nr 4, PP 728 - 731
(USSR)
There are very few experimental data on the compounds mentioned
.1n the t-itle (Refs 1,2). To clarify the structure of these sub-
stances, the infrared absorption spectra of phenyl-, o- and
p-tolyl---, mesityl-, p--diphenyl-, p-ohlorophenyl-, p-bromo-
phenyl-, p-iodophenyl-, as well as a- and P-naphthyl lithium
were measured. These aromatic compounds are crystalline sub-
stances, and not soluble either in hexane or benzene. Therefore,
the spectra of their powders were measured in vaseline- and
fluorated oil. Table 1 shows that in these spectra several new
bands appear which are in a certain connection with the C-Li
bond. The data in table 11, as well as a comparison with spectra
of aliphatic compounds previously described by the authors
(Ref 5), lead to the conclusion that the band in the range of

The Infrared Spectra and Structure of Aromatic SOV120-128-A-26165
Organolithium. Compounds
1045--lo6o cm"' is apparently connected with a free C--Li bond or,
at least, with one poorly participating in the association. The
lower frequencies (870, 970 cm-'), however, may be related with
the C-Li bonds participating in the association. These fre-
quencies characteristic: of "he vibrations of the C.-Li groups
in the spectra of aromatic and aliphatic organolithium com--
pounds, as well as their close position, speak much in favor of
a f-ovalent character of the said bond in the two classes of
comDounds mentioned. Therefore, the assumption of an ionic
character of the C--L_4 bond in aromatic organolithium compounds
lound in publications is incorrect. The authors investigate "t-he
dependence on aromatic compounds responsible for 'the complex
formation of aliphatic compounds of this type (formation of an
intermolecular lithium bond and dipole interaction). In the
present paper, they study not only `,he effect. of the purely
steric factor on the strength of the lithium bond but also that
of the change in the general polarity of molecules. For this
purpose, they introduce other polar groups or atoms into the
organic rest of the molecule. On comparison of the spec_tra of
Card 2/4 phenyl-, o- and p-tolyl-,' biphenyl- and mesityl li-t@hium, it

The infrared Spectra and Structure of Aromatic SOV/20-126-4-26/65
Organolithium Compounds
appears that the degree and type of association of these sub-
stances are different. The CH 3-group in orthoposition has little
affect on the degree and character of association. The same
group in paraposition P-tolyl lithium), however, changes the
spectrum considerably @Fig 1). A complication of the nonpolar
substituent in paraposition equals an extension of the carbon
rest. This reduces the degree of association. The screening ef-
fect becomes most distinct in the spectrum of mesityl lithium.
The symmetrically arranged CH 3-groups render the.association
rather diff.-'Loult. Therefore, only the band of the free C-Li
group at about 1052 cm- 1 is more or less distinctly visible.
Figure 2 shows the spectra of p-chloro-, p-bromo-, and p-io0o-
phenyl lithium. 2 dipoles each - C-Li and C-Hal - are present
in every case. They increase the general polarity of the mole-
cule. This brings about an intensification of the dipole inter-
action between the molecules. The p-ohloro-phanyl lithium is
most intensely and completely associated. The spectra of a- and
Card 3/4 0--naphthyl lithium are different from all other spectra dis-

The Infrared Spectra and Structure of Aromatic
organolithium Compounds
SOV/20-128-4-26/65
cussed. The band is most intensive at 943 cm-1 while little
intensive bands are present a' 1050 cm ..1 - In crystals, these
two substances are' apparently in a mainly associated state.
There are 2 figures, -1. table, and 5 references, 3 of which are
Soviet.
ASSOCIATION:
Nauchno-issledovatellakiy f-.ziko-khimichegk-)-y institut im.
L. Ya. Karpo-ia (Scientif--c Physicoohemical Research Institute
imeni L. Ya. Karpov)

cp
"4&7
s.-,3,200 t-9)
'...Anik-, 0. V., T.141.y.,A. T. Y.,
r
Kochashkov, K. A., Car-"--mpoR-i-m-g--1rTmTor AS U353
TIT12t The Infr-red Spo.tm and Structure Of AO.tyl..id.a of Llthlua
PERIODICA1, Dakladr LksAO-ii mak $333, 1959. Val 129, Ir I$ Yp 121-124
(USSR
AJSTRACTs Ao.tyl*m ta,dri,.tivq. 0& fqm co.ple... with ..Oh D%hr
and with :'modrel 0 y4ft to by .N . of the hydrog.. bonA a. .4
interaction of Sr-loatrons of the group, - C C - (34f 2)-
It could be ass-ed that the substitution of hydrogen at
by one lithius, .%am in oetyl.n. and "Otyla. d4ri-tl- -Zlth"
he aid or .1satrons or the C-U bond eml the at %.I
C;-_ C group .111 Incromso the -.-pl-x-fQmLJ'J O-Pacity Of th...
0 pounds. In order to explain the f b
stmat= at 111tir
:po=da the author. Investigated the spent . f a 1, 1 up "t
::Nylouid., lithium sthylma.tyl.nid., lithlun
litbiu. t rtiu7 b.tylaostylonlde, ad lithi-
spectra 0; sa.tylenld.o -4 of p.tas.t- ..t
sodium eta. a" plotted in co.p.rLsan. Th. --.1t. --
Card 1/2 figures 1 and 2 and table 1. Th. paper under "view 7,ravel ti@-
.1 lithium "OtTlenide. in or7stla fare A-&bj.
::-Pl-xos (aaeora-) with -44h other a. vall -. with other
!pOuAdA Th recardod bonds On.- 1060 &ad 1080 -W" -Y be
'CA-d ;0 t&h* valence vibrations of %he group. =.g C _ LI ...
the complexes. The fr'qu*WY of the 'old - 1br:1.1- of
free group .AM C- LI 8-0-4 to be 1200 a.', . .,
the a . . be. ".4 &.a
"a of lithim PhsDYlA4QtylenIdo. Thus the authors'
=PtiOu (R-r 6) that lithium eastyloaldom &how a stronger
-domay toward. a..Vl.x formation than acetylene Itself As% %,qz
proved. Thi a "Y,b- --plela4d by Imar.seed polarity e
C -I` b.Ad-(c--W-d with RMC - 11) .8 -.11 .. by
peration of am valean. 41.otr.. of the lithlue, atoe
AS the p-arbit. There are 2 figaro.g I table, and
r4f6r4flasmv 4 Of vhiob are Soviet.
LOSOCIATIONg la"hbo-lw. J.dov.t.l-.Jciy ftmIk.-khiaj1h..kIy in.tit.t I.,
1. To. xarpova (ScirtiflG FhY-IQO-ch6sI-41I Research ll,titule
I"nI I. Va. rarpo'
BVMTTJMI July 6. 1959
Ccxd 2/2

PHASE I BOOK MCPL401TATION 3OV/4186
Akadsaiya nauk SM
Stroyeniye veshchestva I spektroskoplys (structure of Matter
and Spectroscopy) Moscow, lzd-vo AN SWR, 1960. 113 P.
Errats. slip inserted. 2.300 copies printed.
'
r. Polenova.
td.t K. V. Astakhov, Professor.' Tech. Zd.s T.
This call atIon of tielon to Intended for physicists
"
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Apoctroscople methods or research
P
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an the structure of molecules &M related problems.
COVMWls The Artielts contained in this eo2lection'wors
taken from the editorial flies of the Zharnal fizzicheakoy
khimii (journal or Pbyaic&l Chemistry) and Are concerned
with spectroscopic zwthods In research on the strt;oture of
molsules, the hydrogen bond, Isotopic effects . problems
Ln magnotoobemistry, the structure or aqueous solutions or
alectrolytes, and the ch*mlatry,or coaplex compounds. Rotor-
once& accomoany individual articles.
Pivovarov. V. M. and _N,__D-.
0rdgF_nts4vA. Postures of Spec
,
trosoopic Manife
In o J@r
,,
station o ran 56621 In'n-Nitroanilim;
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Th*'& th " thank 'to. S. Bobovich And V. S. Reporent for
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A"Inkt-1--14 and To. K. Perealerd [KhimIko-farnatsevti_
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acylated Heterocyclic Amino$ 26
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YA. "Ka
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lologlohasxoy 1. zellt3ln3koy khImll A" SSZR clostitub" or
Unlogicaa and M*dlcal Chemlstr7 of the Academy of K@Iical
sciences USS31. rateraolecular, interstztl= and Oscillation
Spectra or Acotylone Compour4a 36

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Xnstltuts Iment V. P. fttemkln)). Absorption Spectra of
Derivatives of 53
Rabinovich I.. B. tOorlkovskly 925,.J*r3tvennyy unlversiter
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H. 1. lobachev3iQl . Efrect or Displacement or Kydrogmn by
Do uterium on Wis "132 Volume of Liq-11,13 c2
card 3/6
to

S104@16010241006101910301XX
B010067
AUTHORS3 Nurmukhametov, R. N., Shigorin, D. N., and Dokunikhin, N. S.
Luminescence of Solutions of Thioindig-"
TITLEa o and Its Two
Derivatives at 770K
PERIODICAL: Izvestiya Akademii nauk SSSR. Seriya fiziche3kaya, 19609
Vol. 24, No. 6, Pp. 728-729
TEXT: A method of producing luminescence spectra and a long-wave ab-
sorption line with a distinct structure (Ref. 1), developed by E. V.
Shpollskiy and his collaborators with aromatic hydrocarbons was extended
by the authors to compounds with heteroatoms. Data are presented on the
study of the spectra of thioindigo, 5-51-dimethylthioindigog and 6.61-di-
ethoxythioindigo which have a certain solubility in n-hydrocarbons. The
solutions of these compounds frozen at 770K yielded spectra with a distinct
vibrational structure which, in the series of the solvents - from hexane
to nonane - gradually became blurred. An absorption spectrum was obtained
also for thioindigo in n-hexane. The relatively simple spectrum must be
ascribed to the transition of the I-electron in the "-C=C\ group.
Card 112

Luminescence of Solutions of Thioindigo S/048/60/024/006/019/030/X)r-
and Its Two Derivatives at 770K BO13/B067
Although the thioindigo molecule contains four heteroatomag the,.Iong-wave
absorption and emission spectra are caused by the JT-@V-transltion and
not, as usuali by n---ijT*. The alcoholic solution which does not luminesce
at all at room temperature, has a blurred emission spectrum at 770K. Re-
garding its position, it is in agreement with the spectra of the n-hydro-
carbon solutions. The similar behavior of alcoholic and neutral solutions
indicates that the deactivation of molecules in alcohol is not only de-
termined by H-bridges. A detailed description and analysis of spectra in-
fluenced by media with different intermolecular hydrogen bonds are given
in Ref. 8. The present paper was read at the Eighth Conference on
Luminescence (Molecular Luminescence and Luminescence Analysis) which
took place in Minsk from October 19 to 24, 1959. There are 8 referencesj
4 Soviet, I German, and 1 US.
ASSOCIATIONs Fiziko-khimicheskiy institut im. L. Ya. Kaxpova (Physico-
chemical Institute imeni L. Ya,_Karpov)
Card 2/2

�HIGORIN, D.N.; SHOILEGLOVA, N.A.; DOKUIKTIIN, N.S.
Luminescence spectra of halide derivatives of anthraquinone in
frozen solvents. Izv.AN SSSR 24 no.6:778-?81 Je 160.
(MIRA 13:7)
1. Fiziko-khimicheakiy institut imeni L.Ya.Karpova.
(Anthraquinone--Spectra).

NURMUKHAMRTOV, R.N.; SHIGORil.."; DOKUNIKffIN, N.S.
Luminescence of thioindingo solutions at low temperatures. Zhur.
fiz.khim. 34 no.9:2055-2059 S 160. (MIRA 13:9)
1. Fiziko-khimicheskiy institut im. L.Ya. Karpova.
(Thioindigo)

67898
S/020/60/130/06/029/059
AUTHORS; Piskunov, A. K., Shigorin. D. N.' B000007
Smirnova, V. I., S'tepanov, . I. I
TITLE: The'Electron Paramagnetic Resonance Spectra of Some Chelate
Compoundslof Copper
PERIODICAL. Doklady Akademii nauk SSSR, 1960, Vol 130, Nr 6, pp 1284 - 1287
(USSR)
ABSTRACT: The authors investigated the e.p.r. spectra of the chelate
compounds of copper with various azo-compounds as well as with
the enol-form of acetylacetone and acetoacetic ester. Measure-
ment of the magnetic moments showed that copper foms the o=pouna
with two valence electrons. If the initial state of the Cu-
atom is d9sp, it must have an unpaired electron. As, e.g.,
copper forms four equivalent bonds with acetylacetonate, it
is presumed to enter into direct interaction with the N-elec-
trons of the entire system. An investigation was carried out
with the purpose of finding out whether the unpaired electron
of the metal remains localized on the Cu-atom or whether it is
delocalized in the molecule. Table 1 gives the experimental
Card 1/3 data of the compounds investigated: The width 4@H of the line

67898
The Electron Paramagnetic Resonance Spectra of S/020/60/130/06/029/059
Some Chelate Compounds of Copper B004/BO07
gicheskiy institut im. D. I. Mendeleyeva (Moscow Chemical-
technological Institute imeni D. I. Mende@@evy
PRESENTED: August 18, 1959 by V. A. Kargin, Academician
SUBMITTED. August 15, 1959
Card 3/3

81416
141 .3 0 B004/BOO5
..D..,@N.,,,Shcheglovag N. A.2 Dokunikhine N. S.2
AUTHORSg -S@i@rin
Puchkovq V. A.
TITLEa The Nature of the Hz!j@en@Bqitd and Its Influence on the
Electron Spectrum of Molecules
PERIODICALg Doklady Akademii nauk SSSR, 1960, Vol. 132, No. 6,
pp. 1372 - 1375
TEXTs In the introductiong the authors discuss data published on the
influence of the hydrogen bond on the vibration spectraVof molecules,
mentioning papers by N. D. Sokolov (ReE-Tj-and @A.N. F@umkin (Ref, 5).
Then, they investigate tne copianar system of a-nydroxy anthraquinone
in which a n-electron interaction takes place, and the NO group 17s
decisive for the electron excitation. The authors assume the formation
of a quasiaromatic ring by means of the H-bond (Fig. 1). The -1mvestiga-
tion of the electron vibration spectra of this compound and some of its
derivatives yielded the valence vibration of the C-0 group in the basic
state. On abzorption of a light quantum, a change in the distribution of
S/020/60/132/06/41/068
Card 1/3

81416
The Nature of the Hydrogen Bond and Its 3/020/60/132/06/41/068
Influence on the Electron Spectrum of Molecules B004/BO05
the electron densityp of the interatomic distances, etc. occurs which may
lead to a solidification of the ring containing the H-bond (0-H .... O-C).
In the excited stateg the action of the p-orbit of the H-atom becomes more
probable. The rate of transformation of electron energy into vibration
energy, and the probability of a redistribution of vibration energy on
sublevels increase in this connection. The life of each excited vibration
is reduced, and the luminescence spectra of the compounds containing the
H-bond have a blux-red fine structure. This is confirmed by the
luminescence spectra of 1-hydroxy-p 194-p and 1-5-hydroxy anthraquinone
which in fact show no fine structure (Fig. 2p insert after p. 1341)- The
luminescence spectra of a-metbyl-, a-methoxy-9 and a-phen,71 anthraquinone
(Fig. 2) having no H-bond show a fine structure. The data of the spectra
are compiled in Table 1. The difference between absorption- and emission
spectra is discussed; it is explained by the circumstance that the
structure of the mo.lecule and its electronic state change with the
absorption of the energy quantum hyabs; this change is only eliminated
after emission of the light quantum hi emiss . In substances with H-bond,
the excited electron level formed after absorption of hi abe is not
Card 2/3

81416
The Nature of the Hydrogen Bond and Its Influence 3/020/60/132/06/41/068
on the Electron Spectrum of Molecules B004/BO05
identical with the electron level at which emission begins (Fig- 3)-
Coplanarity is a condition for the occurrence of such intramolecular
bonds. The increased interaction of a bridge with H-bond on the basis of
9-(p-hydroxy-)-pheayl acridine investigated by A. N. Terenin and
V. V. Shablya (Ref. 13)9 and the important role of these phenomena in
migration processes of the energy in high7molecular compoundsl(polyamides,
protein, etc.) are pointed out. Levshin's law of mirror symmetry is
mentioned. There are 2 figures, 1 table, and 15 reierences8 14 Soviet,
1 British, and 1 US.
ASSOCIATIONs Fiziko-khimicheakiy institut im. L. Ya. Karpova
(Physical-chemical Institute imeni L. Ya. Karpov)
PRESENTED.- February 119 19609 by A. N. Terening Academician
SUBMITTEDe February 14, 1960
Card 3/3

81733
3/020/60/133/01/49/070
B004/BO07
AUTHORS8 Shigorin, 1). N., Rodionovs, A. N., Talalayevap T, V09
Koche--s-WdV-,--K,- A.9 Corresponding Member AS USSR'
TITLE& An Investigation of the Nature of Secondary Chemical Bonds
PERIODICAL3 Doklady Akademii nauk SSSR, 1960, Vol. 1339 No- 19
PP- 178 - 181
TEXTg The authors defined the formation of secondary (less strong)
chemical bonds as an additional interaction of the valence electrons
caused by a change in the energy-state of the electrons in the total
system of chemical bonds of the molecule. The formation of secondary bonds
thus does not depend solely on the nature of the atom entering into the
moleculeg but also on the properties of the molecular system and on the
distribution of electron density in the molecule. The authors investigated
the infrared spectra of lithium-organio compoundsqand acetylene I
derivatives. The infrared spectrum of R-Li and Ar-Li compounds shows a
characteristic frequency Iof the valence oscillations of the free C-Li
group at 1050 - 1100 cm- . Measurement of the dipole moments of R-Li
Card 1/4

81733
An Investigation of the Hature of Secondary S/020/60/133/01/49/070
Chemical Bonds B004/BO07
compounds in hexane gave the electric moment of 1.1 - 1.2 D for C-Li. The
existence of oscillation frequencies and the low dipole moment indicate
the covalence-character of the C-Li bond. In benzene- and hexane solutions
of lithium-organic compounds as well as on their crystals, additional
bonds were found.9 which lack in the vapor spectra, and which are due to
complex formation. Like the compounds of Be, B9 and A19 also the lithium-
organic compounds form complexes by way of a secondary Li-bond. This is
explained by means of the properties which these elements have in commons
free energetically low p-orbite; the possibility of changing the energy
state of the valence electrons in the direction a p with only little
energy. In this wayg polycentric molecular electron orbits can be formed.
These elements form chemical bonds not only by means of their valence
electrons, but also by ceding free orbits to electrons which participate
in the primary bond of other molecules. In the dimeric complex of lithium-
organic compounds every C-atom of the carbon bridge with 2 Li-atoms is
able to form a tricentral orbit (two electrons in the field of three
nuclei). This orbit is more stable than the usual C-Li bond. For the
initiation of the polymerization of ethylene and its derivatives under
participation of R-Li or Al(R) the formation of a complexl(I) is
3'
Card 2/4

8 733
An Investigation of the Nature of Secondary S@ub/60/133/01/49/070
Chemical Bonds B004/BO07
assumed on the basis of these conceptions. Together with V. I. Smirnova,
the authors proved the formation of radicals in the reaction of TiCl 4
with R-Li by means of electron paramagnetic resonance. The formation of
complex (I) is proved by the colored complexes of ethyl lithium with
styrene, (x,- and P-methyl styrene and other unsaturated oompoundsq which
are characterized by an intense absorption band of the C-C bond. The
authors discuss the formation of secondary bonds under participation of
undivided electron pairs in the complexes R-Li ... X (X - 0--9 v::, 3to.)
+S -S
the agn-conjunction Li - C-C-EC- in the compounds of benzyl lithium and
fluorenyl lithium as well as the participation of the O-Li group, O-Al
group etc. in secondary bonds in acetyl acetonates under formation of
quasiaromatio rings with participation of n-electrons.lAccordingly, there
exist various types of secondary chemical bonds, which manifests itself
in the physical properties and in the reactivity'of the compounds. There
are 13 references: 10 Soviet, 1 British, and 2 German.
Card 3/4

81733
An Investigation of the Hature of Secondary S/020/60/133/01/49/070
Chemical Bonds B004/BOO7
ASSOCIATION: Fiziko-khimicheskiy institut im. L. Ya. Karpova (Physico-
chemical Institute imeni L. Ya. Karpo
SUBMITTEDg March 25,, 1960
Card 4/4

,I,S,:,H.IGORI.N,D.N..; SHGHIGLOVA, N.A.; DOMIKHIN, H.S.
Luminescence spectra of halo derivatives of anthraqninone
in frozen solutions. Dokl.AN SSSR 133 no.2:420-44-3
J1 160. (MBA 13:7)
1. Fiziko-khimicheskiy institut imeni L.Ts. Karpova. Fred-
Btavleno akademikom A.K. Tergninym.
(Anthraquinone--Spectra)

SHIGORIN, D.N.; POMEMTSEV, N.M.; SUMIN, L.V.
Characteristics of the proton magnetic resonance spectra of the
oe- and P forms of polypeptide chain . Vysokcm.w ed. 3 no-4:560-
561 Ap 161. (MIRA 14:4)
1. Fiziko-khimicheakiy institut imeni, L.Ya.Karpovae
(Peptides) . (Nuclear magnetic res.onance and relaxation)

GASTILOVICH, Ye.A.; SHIGORIN, D.N.; GRACHEVA, Ye.F.; CREKULAIEVA, I.A.;
SHOSTAKOVSKIr-, -M.F.
Investigating the nature of the complexes and derivatives of
acetylene by the method of infrared absorptionfispectra. Opt.i
spektr. 10 no-5:595-599 My 161. (MIRA 14:8)
(Acetylene---Spectra)

SHIGORIN D.N.- KOZLGV, YU.I.
Study of free radicals of the triphenylmethyl group with the aid
of their luminescence spectra. Opt.i spektr. 1Q, no.5:600-606
My 161. (MIRA 14:8)
(Trityl group--Spectra)

? 0 . 1)
I,M,;T-U",-,.-IT V, RX.; SHIG0.U?:j D.R.; KOZILV, Yu.I.; PUCHKOV, V.A.
Effect of the hydrogen bond on Vne luminescence of hydrox@- .-.
and amino azo compounds. Opt. i spoktr. 11 no.5:606-
612 11 161. (MM, .14:10)
(Azo coripcunds--oSpectra)

I NURMUKHAMESOV, R.N. (Mbskva);.-SH!Q.ORI@, D.N. (Moskva)
-nature of the luminescence spectra of anthraquinone and its
JS -derivatives in frozen solutions. Zhur. fiz. khim. -35 no-1:
72-79 Ja '61. (MM 14:2)
1. Fiziko-,khimicheskiy institut im. L.Ya.Karpova.
(Anthraquinone--Spectra)

S/020/61/136/002/024/034
B016/BO60
AUTHORSt Rodionov, A. N., Talalayeva, T. and
Kocheshkov, K. A., Corresponding Member AS USSR
TITLEt Study of the Structure of Complexes of Organolithium
Compounds With Ethers by Infrared Spectra
PERIODICAL: Doklady Akademii nauk SSSR, 1961, Vol. 136, No. 2,
pp. 369-372
TEXT: The authors wanted to clarify the effect of ethers upon the
structure and the character of complexes of organolithium compounds with
the ethers. For this purpose they took infrared absorption spectra in the
two-beam spectrometer type H -800 (N-800) featuring a NaCl prism. The
following compounds were examined: methyl-, ethyl-, n-butyl, phenyl-,
o-, m-, and p-tolyl, p-Cl- and p-Br-phenyl-, mesityl-, and fluorenyl
lithium as well as the etherst (C2H 5)201 (n-C 3H7)20' ('so-C3H7)20'
(n-C4H9)2O, and (iso-C 5H11)20' Table 1 gives the vibration frequencies
Card 113

Study of the Structure of Complexes of S10201611136100210241034
Organolithium Compounds With Ethers by B016/BO60
Infrared Spectra
(cm-I) of the C-Li bond in fresh solutions of the mentioned organolithium
compounds in the five ethers. Some of the former were synthesized directly
in the respective ethers. The authors compared the spectra with the data
obtained from their previous studies (Ref. 1) and in this manner assigned
the absorption bands to the vibrations of the C-Li...O groups. The con-
clusion is drawn from an analysis of the data in Table 1 that almost all
of the fresh solutions of the 11 substances mentioned display a similar
spectrum in the same ether. The replacement of one ether by another has a
remarkable effect upon the position of the C-Li ... 0 group bands (Fig. I B).
The analysis of the spectra proves that the more complicated the radicals
used in the ethers, the farthez the C-LJL ... 0 bands will be shifted in the
region of shorter waves. It is inferred from results obtained that during
the dissolution of organolithium compounds in ethers the primary com-
plexes are deformed and decompose due to an acceptor-donor interaction
and a dipole interaction with the ether. Subsequently, new complexes
according to the acceptor-donor type
Card 2/3

Study of the Structure of Complexes of S/020/61/136/002/024/034
Organolithium Compounds With Ethers by B016/BO60
Infrared Spectra
Li Li + 0 Li Li*O ->R-Li... 0 + R-Li.
R R R Ri R1
are formed (depending on the structure of the radicals of the two com-
ponents) between the molecules of the ether and the organolithium. com-
pound. In this connection, the polarity of the C-Li bond is increased with
increasing stability of the new complexes. In the authors' opinion, this
is bound to express itself in a change both of the reactivity of the
organolithium compound and its stability in the solution. This circumstance
is believed to be the cause of the high activity of ethyl lithium in many
reactions in the ethereal medium as well as of the poor stability of this
substance in.the-same medium. There are 2 figures, 1 table, and 8 ref-
erences: 4 Soviet, 3 German, and I British.
ASSOCIATION: Fiziko-khimicheskiy institut im. L. Ya. Karpova (Physico-
chemical Institute imeni L. Ya. Karpov)
SUBMITTED: September 14, 1960
Card 3/3

S/020/61/136/003/018/027
B016/BO52
AUTHORS: Simonov, A. P. Shigorin D. N., Talalayeva, T. V., and
K. A.@,Cr`rspon @,n ember AS USSR
Kocheshkov,
TITLE: Examination of the Structure of Lithium Alcoholates by
the Method of Infrared Absorption Spectra. O-Li...O Bond
PERIODICAL: Doklady Akademii nauk SSSR, 1961, Vol. 136, No. 3,
pp. 634-637
TEXT: The authors examined the structure of R-O-Li bonds:
tert.-C 4H9OLi, CH3OLi, C 2H5OLi, n-C3H7OLi, and n-C4H9OLi. By measuring
various properties of tert.-C4HqOLi (under the collaboration of V. N.
Vasillyeva, V. A. Dubovitskiy, and 0. V. Nogina) the authors found that
the O--Li bond of tert.-C4H9OLi is of a co-valent character, and the latter
associates already in weak solutions. This was proven by infrared spectra
in crystallized state and in solutions (Table 1). In hexane, CC14,
cyclohexane, dioxan, di- and triethyl amine, these spectra hardly differed
from those of the crystallized sample. Therefrom, and from the
Card 1/3

Examination of the Structure of Lithium S/020/61/136/003/018/027
Alcoholates by the Method of Infrared 13016/BO52
Absorption Spectra. O-Li...O Bond
indifference of tert C H90Li toward active solvents and temperatures
'_ 1he authors conclude that its complexes are very
between + 70 and -800C
constant. They attempted to explain the existence of such solid complexes
as follows: 1.-"ree-center intermolecular electron orbits are formed due
to the fact. that the Li atom of a molecule gives the free p-orbit to those
electrons which take part in the O-Li O-bond of another molecule.
Consequently, one pair of valence electrons takes part in the formation of
two O-Li ... 0 bonds (see scheme Ia); 2. an acceptor - donor interaction
sets in during which the unshared pair of p-electrons of the oxygen atom
uses the free p-orbit of lithium in another molecule and thus additionally
intensifies the intermolecular bond (I b). From the luminescence spectra
cf tert.-C4WLi (crystals and solutions in hexane), the authors conclude
that either one electron changes over from the multi-center molecular
orbit of the ground state into the excited multi-center orbit, or that the
system is excited by the passage of one electron of the unshared pair of
the oxygen atom into the multi-center orbit. The four other alcoholates
studied, were spectroscopically examined in crystallized state (paste in
Card 2/3

Examination of the Structure of Lithium
Alcoholates by the Method of Infrared
Absorption Spectra.
S1020V611136100310181027:
B016/DQ52
0-Li.,,0 bond
vasvline or fluorinated oils) (Table 2)..Sinae tert '-Cj'Hq0Li is closely
'
associated, the authors conclude that lithium alcohola es afid unbranched -
J4@"-41
aliphatic radicals are even more closely.qpsociated. This explains their
insolubility or low solubility in solvents in which@ iert 0 H OLi is easily.
*- 4
2 1
soluble. The authors approximately assigned the bonds of the our latter
alcoholates to the complex oscillations of the associated.0-Li groups.
A more accurate assignment, however, will become possible by further
investigations. There are 2 tables and 21 references: 4 Soviet, 1 US,
British, and 2 German.
ASSOCIATION: Fiziko-khimicheskiy institut im. L. Ya. Karpova (Physico-
chemical Institute imeni L. Ya. Karpov-)
SUBMITTED: September 14, 1960
R R
.
.....
Lf (0

Card-3/3 ------

FISKUROV9 A.K.; SgGORINO D.N.; STEPANOV9 B.I.; KLINSEPWv E.R.
Paramagnetic resovan e of solutions of certain o3Wazo qopper
compounds. Dokl. AN SSSR 136 no.4,871-874 F 16le (KMA 14tl)
1. Fiziko-khimicheskiy institut imeni, L.Ya. Karpova i Moskovskiy
khimiko-tekbnologicheakiy institut imeni D.I. Mendeleyeva.
Predstavleno akademikom V.A. Kargimym.
(Copper compatnds-Spectra.)

23857
S/020J6!/137/006/019/020
B101/B201
-4 0 3 7, //,? f/ / -3 ?-f)-
AUTHORS: Shigorin, D. N., Shcheglova, N. A., and Dokunikhin, N. S.
TITLE- Expressions of the autonomy of electron groupings in
luminescence spectra of complicated molecules
PERIODICAL: Doklady Akademii nauk SSSR@ v. 137, no. 6, 1961, 1416-1419
TEXT: A quantum-mechanical study of the electron levels of simple molecules
with multiple bonds has yielded the following results: 1) excitation is in
relation with the participation of n- and p-electrons of the chromogenic
groi@p (:@:C=C4._-, C=01 etc.), on whose energetic state the substituents (auxo-
chromes) bear an influence. The authors of the present paper wanted to
clarify the problem as to whether the autonomy of electron groupings
(chromophores) appears both with absorption and with emission (luminescence@
The luminescence spectra of complicated molecules were examined, such as
anthraquinone (II), phenanthrene quinone (*III). and anthrone (iv), as well
as thioindigo and its derivatives@ The investirration was conducted at
concentrations of lo-4-lo-5 mole/l in n-paraffins. T = 770K. Results are
presented in Fig. 1 . For II I its a- and P -monohalogen- @ a-methyl- , a-phenyll
Card 1/*i

23857
S/020//@ 1 /137/0006/0191020
-41 'D -, 4,-
Exoressions of the - ' --j-1
and a-methoxy derivatives, as well as for III and 1V the following was
found: the distance between the intensive bands and t-'--.e weak bands amounts
to 1664 em"I (for III and IV 1686 cm-1) iorrespopding to the frequency of
stretching vibrations of the chromophore C=O group. Fbr mesobenzanthrone,
its tono- and dibromo derivative, and for thioindigo the fine structure is,
in accordance with E. V. Shpol'skiy (UPT, 68, 51 (1959); jl@ 215 (1960))
characterized by the frequencies of the sym:::etri@@ vibrations of condensed
aromatic rings, and not by the frequencies of the strRtching vibrations of
the C=O group, which, consequently# does not act as chrom-ophore in these
compounds. It is inferred from the foregoing that an unequivocal autonomy
of"electron groups (chromophores) appears both in the absorption and
luminescence spectrum of complicated molecules. These effects are best
observed at low temperatures, since at higher temperatures the spectrum
becomes unclear due to transformation of electron energy into vibrational
energy of the rings. For molecules with two chromophore groups at low
temperatures it has been noted that depending on the conditions of excita -
tion (;@, temperature, medium) either electron state, but also both spectral
may be observed, A further fact that corfirras the conservation and the
strengthening of hydrogen bonds in oL-.hydrf)xy derivativ--@s of anthraquinone in
Card 2/6

23857
S/020/61/1 37/006/010/020
Expressions of the ...
tile excited ut-ate is the luminescence spectrum of 1, 4, 1q, 8-tetrahyaroxy
r
anthraquinone Bach C=0 r-roup participates in t--ao 11 bo nds, so that four
addi-t4-Ional quasiaromatic a quasi-corona
0. 00
t I I
Al @,-'
(X) for:23.
Y, TO 1,
. . 0
0 W 0'A'
The spectrum of this compound di-splays frequencies sim--ilar to those of the
corona as well as frecluenc-'es that are characteristic of anthracene. A
cliz-omophore system is formed which comprises rings with .H bonds, and In
--:hi c' I,, e n re
h the frequencies o:E -I"he stretch--;ng vibrations of t- C=O E--ou-,s a no
@iore ;2--term--7-ia'4ve. The sjjecttra of P-substituted anthraquinone (3.-j T
R-C-@=O) a!'-o-., th.e conclusior to be drawn that (under adequate condf-tions of
@:-.c--*tation) +Ie intersit-v of tl-.e Rar.-.an band of tl@,? chromoz2hore (C=O) ard th-e
intens-ity, conresnondiinE to "he 011 - 01 transition in the lumi-nescence s-,nec-
truTII , ch--Yi_re. To c'onclude: 'local, 'Imt1ticentered" 6-lectron o b-+@ -;.y ise
ar-
4 t h t.he participatior of n electrons in complicated molecules. . Academician
Card 3/6

23857
S/020/61/137/006/019/620
@Ixpressions of thek B101/B201
anked for discussions. There are 1 figure and 11 re-fFer-
.@A. N. Terenin is th,
ences: 10 Soviet-bloc and 1 non-Soviet-bloc. The reference to EnClish-
language publication reads as follows: E. Y. Bowen, B. Brocklehurst, J.
Chem. Soc 1954, 3875.
V@
ASSOCIATION: Fiziko-khimicheskiy institut im'. L. Ya. Karpova (Physicochemi-
cal institute im. L. Ya. Karpov)
PRESETITED: Nov*aber 9 , 1960,by A. N. Terenin, Academician
SUMITTED: November 2, 19@6
Fi&. 1. Luminescence spectra of anthraquinone deri@vatives in heptane at
770Y.
Le end: a) @' F9 - 313 mg; ..6 Hg @ 365 mii; 1) a-chloroanthraouinone; 2) 1
dihydroxy anthraquinone; 3) 1, 5-dihydroxy anthracuihone; 4)
tetrahydroxy anthraqui-none (A emission'; 5 absdr-o@--ion); --ithrone (in
ht-a-e) , the sho'rt-,aave i)art of tile spectru-n with
nit 4043 A is not shown;
Card 4/6

28676
S/02 61/140/002/021/023
BI 30YBI 10
A U T H 0 2- D. N. Smirnova, V. I., Zhuravlevay G. S.)
yrr.cheva, Ye. P., and Shostakovskiyt M. F., Corresponding
--iber AS USSR
TITLE: inr zpectra of y-irradiated acetylene and its derivatives
C 7 22
- @kadh7mmi.,.,a nauk SSSR. Doklady, v. 140, no. 2, 1961, J19-4 2
TEXT: To the relationship between the structure of the initial
a--, thD structure of the resulting radical, the authors studied
tho ep-,- I I-ir-radiated acetylene, methyl acetylene, methyl
deute-r',) P4., 1- and butyl acetyline, as well as phenyl- and
thy
meth:yl-,,@bc.-y! ar-,-ityiene at 770K. The compounds were irradiated in
special - - 1, U , -3 giving no epr spectrum W 4 th the used dose of Y-radia-
t i on . r c, the tests, the ampuls were evacuated to jo 3 mm H&. Irra-
diaticn w,-iG -@onducted with Co6o. A superheterodyne radicapectroscope
was used f(:r taking tile epr spectra. The magnetic field was calibrated
with Lh.-, e@'-r s:@eetra of the pyroxylamine disulfone ion, @'O(SO,Wj in
Car d I

28676
5/020/61/140/002/021/023
Epr spectra of y-irradiated B130/B110
during the experiments. There are I figure, 2 tables, and 4 references:
2 Soviet and 2 non-Soviet. The two references to English-language
publications read as follows: C. P. Poole, S. Anderson', J. Chem. Phys.,
31, no. 2, 346 (1959); R. West-, Ch. Kreinzel, J. Am. Chem. Soc., 84@
no, 4, 765 (1961).
ASSOCIATIOTIT: Fiziko-khimicheakiy institut im. L. Ya. Karpova (Physico-
chemical Institute imeni L. Ya. Karpov)
SUBMITTED; May 25, 1961
Table 1. Integral intensity of y-irradiation ^,107 rad.
Legend: (a) initial compounds (boiling point, OC ) (b) radical presumed,
(c) number of lines, (d) total width, oersteds, (e@ the number of lines
due to superposition with the spectrum of CH 3- CzC-H cannot be determined.
Card 315

SD40NOVJI A.P.; SHIGORIN, D.N.; TALUAYEVA, T.V.; KOCHESEXITi, K.A.
Infrared absorption spectra of some R - 0 - Li compounds.
Dokl. AN SSSR 141 no.3:665-667 N 161. (IMA 14:11)
1. Fiziko khimicheskiy institut im. L.Ya. Karpova. 2. Chlen-
korrespondent AN SSSR (for Kochedhkov).
(Lithium organic campounds-Spectra)

SIMDNOV, A.P.; SHIGORJN, D.N.; TALALAYEVA, T.V.; KOCHESHKOV, K.A.
Association of tert'C-H,,OU in the gaseous state. Izv.AN SSSR.-
Otd.khim.nauk no.6:1& -62. (@@.A 1518)
1. Fiziko-khimicheskiy institut im. L.Ya.Karpova.
(Lithium butoxide-Spectra)

SHIGORIN, D.N.; VOLKOVA, N,,V.,-. FISKUNOV, A.K.; GUREVICH, A210-
Studying the triplet states of molecules by the methods of
himinescence and electron paramagnetic -resonance. Opt.i spektr.
12 no.5.-657-659 14Y 262, (IMIRk 15:5)
(Mlecular dynamics) (Taimi scence)
(Paramagnetic resonance and relaxation)

SHIGORINY D.N.; NURMUKRAMETOV, R.N.; KOZLOV, Yu.I.
laminescence of indigo solutions at 770K. Opt.i spektr. -12
no.5:659-661 Yv 162. OMM 15:5)
(Indigo) (Luminescence)

MMOIAYEV.. V.L.; SVESHITIKOVA, Ye.B.;-SHIGORIN, D.N.
Nonradiative energy transfer between the triplet and singlet
states in organic moloculesl discussion of A.N.Terenin and
V.L. Eriholaev's report "Inactivation of the triplet btate
in aromatic molecules". Izv. AN SSSR. Ser. fiz. 26-no.l*.29-
31 Ja 162. (KR& 15:2)
Organic compounds)
lecular dynamics),
k

SIMONOV.9 A.P.; SHIGORIN, D.N.; TALAIAYEVA, T.V.; KOC=I@KOVJK.A.
Study of the lithium alcoholate structure by the method of im . 6@@
X@+
absorption spectra; O-Li ... 0 bond. Izv. AN SSSR.Ser.fiz. 26 no. @
124&-1249 0 162. (MIRA 15:10)
(Lithium alcoholate-Spectra)

SHCIT-EGLOITA, N.A.; SHIGOPIN, D.N.; DOKUNVTIN, N.S.
Luminescence of monohalo derivatives of anthraquinone in frozen
solutions. Zhur. fiz. khim. 36 no.9sl938-.1946 s 162.
(MIRA 17:6)
1. Fiziko-kh-Imicheskiy institut, imeni L.Ya. Karpova, Moskva.

RODIONOV., A.N.,-__SHIGORIN, D.V.; TAIAIAYEVA, T.V.; XOCHESHXOV, X.A.
Structure of complexes formed by aliphatic organolithium-
compounds. Dokl. AN SSSR 143 no.1:137-139 I-L- 162.
(NIRA 15:2)
1. Ch-len-korrespondent AN SSSR (for Kocheshkov)."
(Litbium organic compounds)

LOKSHINt B.V.; PISKUNOV, A.K.; KAZITSYNA, L.A.; SHIGORRI, D.N.
Investigation of the structure of certain inner-complex com-
pounds by means of electron paramagnetic resonance. Dokl.
AN SSSR 143 no-4:867-870 Ap 162. (NIRA 15:3)
1. Moskovskiy gosudarstvennyy universitet im. M.V.Lomonosova.
Predstavleno akademikom A.N.Nesmeyanovym.
(Gomplex compounds-Spectra)

NURMUKHA@ETOV, R.N.; KCZLOV, Yu.I*- SHIGORIN D N ; PUCHYOV, V.A.
Luminescence spectra of azomethine compounds. Dokl. AN SSSR 143
no.5:1145-1148 Ap '62. (MIRA 15:4)
1. Predstavleno akademikom A.N.Tereninym.
(Schiff bases-Spectra)

113/048J63/027/001/007/043
B163/B180
AUTHORS: Kozlov, Yu. 1. , and
TITLE: Formation of free radicals of the triphenylmethyl series
PERIODICAL: Akademiya nauk SSSR. Izvestiya. Seriya fizicheakaya, v. 27,
no. 1, 1963, 14-16
TEXT: Compounds of the following type
R,
-C-R

R R.,
R1
Card 113

3/048/63/027/001/007/043
Formation of free radicals of the B163/B160
were studied , where d ii, oH, M, , H C; R H, N(CH N(C2 )2'
@.3 3)2' il@
R2 = H, Cl, OCH 39 NO2 R3 = H, OCH 3* In such compounds, the -,C - R bond
Ibreaks under ultraviolet irradiation wit)a wavelengths between 250 and
350 m4. The formation of the radicals is prpved by the epr in the
irradiated compounds, and by the fact that the luminescence spectra of
the particles obtained after irradiation of (C6H 5)3C-H'.(C6H 5)3 Ccl,
(C6H5)3 COH coin*cide with the spectrum of.the free tr iphenylm'ethyl radical
obtained by thermal dissociation of (C H )CC(C H ) ' . Before irradiation,"
6 5 6.5 3
the molecules show strong fluorescence at 3800 - 4500 2, and
phosphorescence at 4200 - 4800 it . Both fade as the irradiation time
increases and the intensity of a new fluorescence band at about 5660
increases, which is specific for the resulting radical-s. The
phosphorescence of the initial molecules and the formation of radicals
becomes stronger if the solvent is changed from benzene to hydrocarbons
and, alcohols. Since the energy of radical-formation exceeds the energy
of the exciting quanta P = 313 nm), a direct process is impossible, and
Card 213

S/048/63/027/001/007/043
Formation of free radicals of the ... B163 B180
tne following mechanism is suggested. Pirst there is excitation of the
n-electron system (singlet n-+n.' transition) in the initial molecules.
From, this excited state a nonradiative transition to a triplet state with.
a lifetime of a few seconds is possible. Somi of the molecules in the
triplet state emit their energy in form-of phpspnorescence.quanta, others,
transmit it to the system of a-bonds .7c -A which is weakenedand can
now be broken up by ultraviolet radiation'to form free radicals. The
pr@ bability of formation of free radicals is.lower fo'r gamma-irradiation
thu for ultraviolet. This paper was presented at,t4e 14th Conference on
Spectroscopy in GorIkiy, July 5-12, 1961. There are 2 figures.
Card 3/3

_6/64Y63/627/001/625/043'
ioa 186
B
AUTHORS: Lokshin, B. V., Piskunov, A. K'. ,Kazitayiiaq L. A-9 and
Shigorin, D. N. @j
TITLE: Investigation of the structure-of-some chelate compounds by..
means of electron paramagnetic resonance,
P]@RIODICAL: Akademiya nauk SSSR. Izvestiya. Seriya fizicheakaya''
v. 27, r@o. 1, 1,963,. 75-77
TEXT: The e.p.r.,spectra ofiqeve@ral,.copper complexei formed by the@ aikyll
and aryl imines,of sali-qyl aldehydeq O-OXY ELCetophenone 9 and oxy
naphthaldehyde in the form of:powders and solutions ift.chloroform xere@
studied. The powder,samples disp@ayed one-bifiole asymmetric.absorption
and the solutions showed a hypbrfine struct@r,e (three linds).*:-This
J
splitting is due to the interaction of the unpaired 3a@e*lectron'of
'With the nucleus' of the copper
copper ato@' lmualeqkr@ spin 3/2). . Ah
additional hyperfine splitting into-.five Tin(ej .was 6beerved in the case:'
of copper.o-oxy acetophenone, iminate which-iet,due"to-interaction of.ihe
unpaired electron with two equivalett nitrog'aft -atome (j, I This, oo@td
Card
1/2.

S/048/63/027/001/025/00
B10@/Bl 86
Investigation,of the structurO.,@...
-from the
not be resolved with the other compounds, but was also infe.rred
dependence of the distance betleen the split linea 6n the.structure of thei-
groups around the Cu atom (lipnd). The width of,the e.p.ro lines of the
solid compounds depends on thp exchange intoractigns between the
paramagnetic particles in the,orystal. As the'subs@ituent@'inoreasesf'.
the volume of the molecule and.their steric hindr1kr'be of close packing J!
also increase. This leads to,.areduced volume interaction.and, in the
case of equivalent packing 'the paramagnetic ps, ticleVin the.crystal
of
to a narrowing.of the e.p.r'. lines. There are'2 figures and I table.
ASSOCIATION: Khim.icheskiy-fak*ulftet 'Moskovskog'P@40WO uIUV6rsitbta im,
M. V. Lomonosoira (Chemibal,Br'anoh of 'Noo6ow State. Univer@sit
imeni M. V.. -Lomdn6sov).
Card 2/2

-,44946
i/048/63/027/001/026/043.
B108/Bi86
AUTHORS: Smirnova, V. I.p_Shigqriq_j,;D. A. j.,,@,And Zhuravleva, T. S'*
TIT LE: E.p.r. spectra of gamma-irradiated compounds with multiple.,il-
bonds
PERIODICAL: Akademiya nauk,SSSR; Izvestiya. Seriya fizicheskayal,
v. 27, no. 1-, 1963, 76-80
TEM To establish a relationship between the structure of a molecule
and that of its r@Ldical, the e.p.r. spectra'of gamma-irradiate&
acetylenes and of compounds containing heterocyclic atoms were studied
at 770K. The method used is-deiscribed in a previous paper (Dok1..AN SSSRj:;
140, no. 2, 419 (1961)). The results on the acetylenes are shown in
Table I . The large number of hyperfide lines i's explained by. the
interaction of the unpaired electron -with several protons-.of the sy@steml-@_4,.
3ubstitution of the CH or CH groups by elecironegative atoms in
2
compoundsicontaining 0 or *N atoms changes the,e.liera spectra of the'
radicals. The formation of radicals is associate'a 'with the breakin@g of
the C-H bond of the methyl or methylene groups of the'initial dompobnde*,-@,'
Card 1/4

S/048 63/027/001/026/043
E.p.r. spectra of gamma-irradiated I YBi 66
There are 2 figures and 2 tables.
7
Table 1. Legend: Integral power of irradiation:-1J,10 rad. t boiUng.
point (in OC). width determined from the firs@ derivative of the
-of lines hard to determine because of
absorDtion curve. number;
superposition of the spectrum of not completely detiterized methy
acetylene, spectrum was not-found even at a dose:of 1-40-101 rad)
7
e.p.r. spectrum obtained at a',dose of 1.5010 rad . (1) initial
compounds, (2) assumed radical, (3) number'o'f lines, (4) overall width
of spectrum, oe.
A_
@able 2. Legend: Integral power of irradiation -1.6,10 rad. width
't derivative ofthe absorption our da a.
determined from the fire ve
of the present authqrs. (1)'Inlitial compound, (2) @assiimed radicaly:
(3) number of lines#*(4.) overall width of spectruihl,q'
Card 2/4

S/048/63/027/001/026/043
E.p.r. spectra of eam.-na-irradiated ... B106/B166

HezoAlme coeAurtenmof
nWoonaraemuR PSAUM&n OUR mupm-
da caeKrpa

-k 1,4
5
0,2-
-G=-C-D
II.C
97,5�11

.-Jryttun-8,5@) -cur
Iff,*cr:c-z,
'60), 54 8�'I
71 c. 04:4�2'4@

3 '34 ij
40(12) AIX�4

u
Table 1
Card 3/4

E.p.r. spectra of gamma-irradiated ...
S/04 s/6 3/C)2 7/()@,) 1 /02 6/04 3
BIOB/B186
I '00 FI
t-
T3
IICXOAHUC coeannexua npeAnaaarlemuft paAultai ztnfl@ "
=
0.

11-C11=0
4.- 36 � 1,0
11,c-G-d' 6(8) 86�2,0

CHI-CII-CH I JHjG:'.--CH-GITlj 5 58�1.5
CIIs-G_=N I H. C--- C-:-. N 9 _55,0
:13(15) ''-.64,.0
Table 2

Card 4/4

ACCESSION NR: AT4033990 s/oooo/63/000/000/008)/0086
Shigorin, D. N.; Andrianov, K. A.
AUTHOR: Rodionov, A. N.; Asnovich, E. Z.;@
TITLE: Infrared absorption spectra of some metallic silicones
SWPtE:.-.Geterot"pny*ye-vy*sokomo)ekulyarny-,-ye soyedineniya (Heterochain macro-
mole'cular compounds); sbornik statey. Moscow, lzd-vo "Nauka," 1963, 81-86
TOPIC TAGS: polymer, silicone, siloxane, polyorganosi)oxane, metallic silicone,
aluminum containing silicone, titanium containing silicone, tin containing sillf-yaw,
silicone spectral analysis, polyphenyl slioxane, polymethyl siloxane, polyethyl
siloxane
ABSTRACT; Absorption spectra of polymethyl-, polyethyl-or polyphenyl siloxanes
containip A), Ti or Sn in various ratios to Si were analyzed for the range 400-
11100 cm- . Bands correspondin? to Si-O valence fluctuation in the Si-O-Sn group
-980 cm- those for Sn-O at 530-580 cm-1
were identified at 900 Banci Intensities 77
in these spectral regions varied for all polymers in relation to the netal/Si ratio, R@
indicating preservation of absorption frequencies of the Si-O-metal group dur.'Inc
monomer to polymer conversion. Location of absorption bands for such group vari ed
little from one metal to another. Orig. art. has: 3 graphs, 2 tables,
Crc, - 1/2

ACCESSION NR-. AT4033990
ASSOCIATION: Fiziko-khimicheskiy institut im. L. Ya. Karpova (institute of Physical
Chemistry); Institut elementoorganicheskikh soyedineniy AN SSSR (institute of
Metalloorganic Compounds AN SSSR)
SUBMITTED: o6jui62 DATE ACQ: 30Apr64 ENCL: 00
SUB CODE: OC NO REF,SOV: oo4 OTHER: 003
Card

KOZLOV, Yu. I.; _SHIGORIN. D. IN-
3_-
On the formation of free radicals of the tripheny1mm-tbyl
series. Izv. AN SSSR. Ser. fiz. 27 no.l::L4-:L6 Ja 163.
(MIRA 16:1)
(Trityl group) (Radicals(Chemist@y)j

NURKUKRAMETff, R.N.;-SHIGORIN, D.N.; KOZLOV, YU.I.
Luminescence spectra of solutions of indigo and some of its
derivatives at 770K. Izv. AN SSSR Ser. fiz. 27 no-5:686-689
My 163. (MIRA 16:6)
(Indigo-Spectra)

45146
S/076 63ZO37/002/010/018
Ni 86
AUTHORS: Shcheglova, N. A., _shigox_in_,J1__1L_,_ Ryabchikovaj To S.
Dokunikhin, N. S., Yioiseyeva, Z'. Z. (Moscow)
TITLE: Study of the luminescence spe6tra of some anthraquinone..
carboxylic acid derivatives at low temperatures
PERIODICAL: Zhurnal-fizicheskoy khimi-i, v. 37, no. 2, 1963, 371-37T
TEXT: The luminescence spectra of the following compounds were studied in:
n-hydrocarbon solutions or in the powder: anthraquinone-a-carboxylic acid:-.
and its i.,iethyl ester, anthraquinone-p-carboxylic acid and'its methyl ester,
anthraquinone-1,4-dicarboxylic acid and its dimethyl and diethyl esters
7-chloro-anthraquinone-2-carboxylic acid and its methyl ester, 7-fluoro-
anthraquinone-2-carboxylic acid and its methyl est4r, 6-fluoro-
anthraquinone-2-carboxylic acid and its methyl ester, and 6-chloro-
anthraquinone-2-carboxylic acid. Results: The luminescence spectra of
the esters and their halogen derivatives at 77 OK have a fine vibratioil
structure. The carbonyl of the anthraquinone ring had the highest
frequency. The multiplicity of the spectra proved to be highly dependent'
Card 1/2

S/076/63/037/002/010/018
Study of the luminesce@ce B101/B186
on the len@gth of the hydrocarVon chain of the solvent (n-hexane, n-heptane,
n-octane, n-nonane) which fact can be used in the analysis of these
compounds. Each substituent being an auxochrome (F, Cl, COOH, COOCH ) has
3
a specific effect on the spectrum, manifest in line shifts and intensit@
changes of the major peaks. The luminescence spectra of the powdered halogen
derivatives of the acids as well as the esters had no fine structure at
77 OK, but a system of narrow bands shifted toward the liDngwave region.- The
interdistance between the centers of these bands equals the carbonyl
frequency of anthraquinone. In powdered 1,4-anthraqui'none dicarboxylic
acid, reversible self-extinction of the luminescence was observed. *This
effect disappeared in dioxane solution. The self-extinction is explained:'
by intermolecular interaction (and photo transfer) of one carboxyl proton-,.
with the j electrons of the oxygen in the anthraquinone carbonyl group,
which effect electron excitation by p ----> n* transition. This assumption.
was confirmed by measuring the IR frequency of the carbonyl group. There
are 2 figures and 3 tables.
ASSOCIATICN: FiziA'-o-khimicheskiy institut im. L. Ya. Karpova
Physicochemical Institute imeni L. Ya. Karpov)
lovemb
SUBMITT': D. er 16, 1961
Card M

KOZLOVY Yu.I.; SHIGORIN, R.N.; NURMLJKHAMETOV, R.N.; PUCHKOV, V.A.
Phototransfer of a proton in the quasiaromatic ring with H-
bonding. Zhur. fiz. khim. 37 no.11:2432-2444 N163.
(MIRA 17:2@-
1. Fiziko-khimcheskiy institut imeni L.Ya. Karpova, Moskva..:,

KOZLOV, Yu.I.; MUROMTSEV, V.I.; PISKUTIOV, A.K., SHIGORIN D.N.; OZEROVA G.A.;
VEREYN, N-.V.
Formation of radicals via the tripje@ state in the ultraviolet
irradiation of frozen solutions of a@omatic molecules. @Zhur.
fiz. khim. 37 no.12:2800-2PO2 D 163. (MIRA 17:1)
1. Fiziko-khimicheskiy institut imeni Karpova.

'SHIGORIN, D.N.; SHAPET'KO, N.N.- SKOLDINOV, A.P..@ RYABCHIKOVA, T.S.
Nature of the hydrogen bond in systems with J/- --electrons and
its effect on the proton magnetic resopance. Dokl. AN SSSR 148
no.5sll4l-1144 F 163. (KRA 16:3)
1. Fiziko-khimichesk4ly institut im. L.1a.Karpova. Predstavleno
akademikom V.A,,Karginym.
(Hydrogen bonding)
(Nuclear magnetic resonance and relaxation)

SHIGORIN, D.N.; SKOLDINOV, A.P.; RYABCHIKOV4- T.S.
DeLtermination of the formation energy of a quasiaromatic cycle
with an H-bond from molecular infrared spectrum data. Dokl. AN
SSSR 149 no.2;341-344 Mr 163. (MIRA 16:3)
1. Fiziko-khimicheskly institut im. L.Ya.Karpova. Predstavleno
akademikom V.A.Karginym. . . .
(Hydrogen bonding) (Molecular spectra)

LWHINJ, B. V.; FISKUNOV, A. K.; KAZITSYNA, L. A.; SHIGORIN, D. N.
Anmly-sis of the structure of certain che-late compounds by the
el@ctron paramagnetic resonance method. Izv. AN SSSR. Ser. fiz.
27 no,1:75-77 Ja 163, (MIRA 16:1)
1. Khimichesldy fakulltet Moskovskogo gosudarstvennogo uni-
versiteta im. M. V. Lomonosova.
(Cholates--Spectra)
(Faravegnstic resonance and relaxation)

�_4@GORIN, D.N.; SHCHEGLOVA, ff.A.; PISKUNOV, A.K.; OZEROVA, G.A.;
DOKUNIKHIN, N.S.
iyzectrons. Dokl. AN SSSR 150 no.4z862-865 Je 163.
(NMA 16:6)
1. Fiziko-khimicheskiy institut imeni L.Ya. Karpova.
Predstavleno akademikom A.N. Tereninym.
(Molecular spectra)
(Hydrogen bonding)
Ro- onds In excited elect, ic s-tates of molecules with

L 32069-66 EWr(m)/E7dP(J) RM
-ACC NR: An6oi.6112 SOURCE CODE: im/oo58/65/oO0/OlVDO12/J)012
AUTHOR: ShIgorin, D, fi. Shchwloya. N. A-; PlskuncMA Ak _L: Oz G. A.
_TTTLE: Hydrogen bonds in excited electronic states of molecules witWir ctrons
SOURCE: Ref. zh. Fizika, Abs. 1ID83
REF SOURCE: Tr. Komis. po spektroshopii. AN SSSR, t. 3, vYP. 1, 1964, 302-312
@TOPIC TAGS: hydrogen bonding, excited state, absorption spectrum, luminescence Bpec-
,trum, nonmetallic organic derivative, conjugate bond system, ground state, lumines-
-cence quenching
ABSTRACT: On the basis of data* on the absoxI)tion and luminescence spectra of cr-oxy-
'and methoxy-derivatives of anthraq!@@cnejit is shown that the energy of production of
the hydrogen bond in the excited state increases compared with the ground state by a
factor of almost 2 and reaches 15 kcal. The increase in the energy of the H bond in
the case of excitation with c?nJuRat bonds:Vis connected with the increase of the
energy of the n-electron. interaction in the quasiaromatic cycle, formed with parti-
cipation of the p-orbit of the bydrogen atom of the X-H group. The question of the
role of the H bond in processes of deactivation of the triplet state"and luminescence
quenching is considered. [Translation of.abstract]
SUB CODE: 20, 07

.ACC NRs AR60161TT SOURCE CODE: UR/0055/65/000/0231DO14/DD14
AUTHOR: OWeEinp D. N.; Gastilavich.,. Yes A.; Komarov, N. V.
stigation of compounds of the 4roup (CF@5).rX-0aCAj,*"vhere X'w C 1, 96)
TITLE: Invii 2-
@.and Pb in the region of valence oscillations of the grouPs-C4 and C-H
Sa=: Ref. zh. Fizika., Abs. 11D97
7
MW SOURCE: Mrs Komis. po q!. -678
Mrookopii. AN SSSR,j, t 3j, V"- l.- Xq&., 67
TOPIC TAGS: absorption band, ir spectrum, complex molecule,, molecular p)Wsical
molecular interaction
j-'AB8TRJCT: The frequencies of the valence oscillation groups Oac and'MC-H in com-
:1;1o'1L1L1t3& (CH3)3-X-0N1H Were calculated. The calcuUted frequencies are cocZared vith
the measured frequencies in ir spectra of the compounds (CH3)3-C-CBM (I)j,
.(CQ3-Si-0KM (II)p and (C2H9)arSn0aCH (In)* It is concluded that in compounds
with J8i,, Go., Sn., and Pb there shcAlld be observed an intramolecular interaction with
participation of the x-electrons$f the C!mC bond, using the d-orbit of the X atom.
The presence of such an intiir@ion is confirmed experiments.13,Y 17y the fact that 9A,
increase is observed in the intensity of the absorption band of the group Cr=C in 11
and in 131 coMared with Ij and that compounds JI wA III foTm strager cowlexes
with an electro-donor solvent: (CV3)3-X-OsCx ---- Y-R. [Translation of abstract]
MM Ca6z..
07.. 20
C

ZHUR-AVLETA, T.S.; PETROV, --.S.; SHJWRJ@j
I., @,, D.N.
Eaectron paramagneetuic resonance spect-.= of the anion, radical
0
of diphenylaceluflene. Zhur. stml,". khim. 5 no.5:78r,-j786
S-0 1@4 OMIPA 18.,l)
1. Fiziko-lihimicheskiy institut imeril L. Ya. Karpova.

ALEKSANDROVA, 1.P.; SHIGORIN, D.N.; SKOLDINOVt A.F.
X-rity ispnctra of quaol-aromtlo Inner-complexas of loppor.
Zhur. fiz. khIm. 38 no.5t1203-1209 My 164. NIRA 18SI2)
1. Fizlko-khimicheskiy institut imeni Karpova. Suba-itted
June 8,, 1963.

:@RCW GD! -
_r - A i , N-,.; @)H IG01UN D. N
. articti- -naphth-@-
I" "ar feaLure5 cf the electronic spectra of 1,4
quinone ard some or i-.s deri-vatives. Zhur. fiz. khIm. 38
no, 5.,1261-1267 M7 1U. (MIFA, 18zl-C,I-
1. Fiziko-kh-4Micheskiy 4nztitul. 4-rieni Karpova. Submitt-@d
Aug@ 9, 1963@

!J152t6
M(J)/EPA(s)-2/EWT(m)1EPF(q
I - N )@ @ITWIWP (J )N@fA WAWA (1) Fci-4/
P9-4/Pt-1Q/Peb__ASD(n@_3/RM '%kFj_ --- -_ - ____
ACCESSION NR: AP4043779 '@"s 7oi 9 -a '/64*7'6orjf&as/i4iL/l4l4
>5 N 4' ;'
AUTHOR: Nurmukhametov R. N. Bandareva, L. V,; ShLsorin, D.
Tokareva, L. G.; Hikhaylov# No go
TITLEt Application of the luminescence method to determine the
state of stabilizing additives in polymers
SOURCEt Vy*aokomolekulyarny*ya soyedimeniyas v. 6, no. 8, 19646@i
.1411-1414
TOPIC-TAGS: di-O-naphthyl-n-p6eu6lonediamtne,.di-i3-naphthyl-mi.0
phone lane di amine antioxidants antioxi'dautp poly-rdpylens ELbe-ri'lf
P
polyamide fiber, di-S-naphthyl-n-phanatenediamine luminescence
spectra, polymer additive, photoozidation Inhibitor, polymer
stabilizer, synthetic fiber
ABSTRAM A study is made of the ab sorptLon and luminescence
spectra of N,H'-di-2-naphthzl-p-phenzlenaditaLne~1(t) used as a
stabili&ing ad ve possessing a light- and hwat-protective action
on polypropyLeMeVand polyamida fibersJrFrou identifications of the
luminescence spectra of ioluttons and fibers containing the addi-
:card 1/3

7..
FACCSSSION NR: AP4043779
tive it was concluded th&t-,a; solid _mol6cdl:ar solutloh:-is' formed wit
the addition of I to the polymire Thit -1 Mirs. "'And; 4olutLOSS contain".
in& I were Aubjected to heat treatmenteadto gamma-kan4"Uttravidlet" L,
radiatiop.PThe consumptLon--of I in the polymers was deterainad by
recording the intensity of the LnL.-Lal fluorescence band. Solutionsl
of I had absorption bands in the near UV region. The primary
I protective effect of I is related to its function as a filter ab-
sorbing the UV section of the light. The photochemical inhibiting-
effect according to Semenov is based on the termination of the re-
action caused by free radicals. With the absorption of light and
gamma quanta, and also with heat treatment, a.molectile.of I gives,
p an electron easily and various "ositive Load and@.Ion radical
u
are formed. As a result of these treatments colored, pro'ducts, are.
formed from 1, it is assuaed;that.the primary photochemical act
-proce
in I was the photoioMLzatioa-4hLc4 ip, areattyl- through the
p
triplet state. From the ease tri-th--which the- hatodmLdation, 6E
',7 coiiclude4 that-- fa-4 strong
molecules of I occurredit can bo-
antioxidant capable of inhibiting photaoxidatLon processes in poly- i
mars* It can be seen from the observed sLailarity in the change of
Card
2[3 7

GASTILOV1CH., Ye.A.; SHIGORIII, D.N.; KOMAROV, N.V.
Use of the method of infrared absorption spectra in studying acetylene
derivatives containing elements of group IV of Men&eleevts periodic
law. Opt.-i spektr. 16 no.1:46-51 Ja 164. (MIRA 17:3)

SHAPETIKO, N.11,; SFTG0 T@7@1, D.N.; SK01-DINOV, A.P.: RYABCIIIKOVA, T.S.; RESFXTOVA,
L. N, --
Chemical shifts Of nuclear magnetic resonance of protons of O--H com-
m
pounds formin- an 1.rLramolecular hydrogen bond of the O--H...0 type.
0
Opt. i spektr. 171 no-3:459-461 S 164. (MIRA 17:10)

ACCESSIO',4 ',qR'. AP4019525 S/0076/64/038/002/0469/0471
AUTHOR: smirnova, V. Is; Zhuravleva, T. S#;.Shigorin, D. N,; Gracheva, Ye. P.
Shostakovskiy, M. F.
TITLE: EPR spectra of some di-substituted acetylenes upon exposure to gamma rays
and to light
SOURCE: Zhurnal fizicheskoy khimii, v. 38, no. 2, 1964, 469-471
TOPIC TAGS: methylphenylacetylene structure, ethylphenylacetylene structure,
dimethylacetylene structure, electron paramagnetic resonance, acetylene, alkyl
radical, acrylic compound, methyl, EPR
ABSTRACT: This is a continuation of a work by the same authors (AN SSSR, Dokl.,
140, 149, 1961) where they described how a number of acetylenes of the Rp..:- CH
type (where R is an alkyl radical) ypon exposure to gamma radiation form radicals
where the unpaired electron is delocalized by the triple bond over ihe whole
molecule. The present work transfers the above study to Ar - C i C - R arylic
compounds of a different structure. The object of the study were: methylphenyl-
acetylene, its deuterium tagged form, ethylphenylacetylene and dimethylacetylene.
Card 112

ACCESSION UR: AP4019525
UV radiation was provided by the SVDSh - 1000 lamp. Gamma doses were 2 to 80 m.
rad. Using the EPR method, the structure of radicals formed by gamma and light
radiation of the above compounds was determined; the radicals are formed by
tearing off a hydrogen.atom from the methyl or methylene group. In these-radicals
the free electron is basically localized in the R group, whereas in the R - B. C
CH2 radical (like the propynyl radical CH a C a CH.) the unpaired electron is
delocalized by the triple bond-over the wMe molecule. Orig. art. has: 5
figures, 2 formulas, 1 table.
ASSOCIATION: Fiziko-khimichaskLy institut im. L. Yas FArpova (Physics and
Chemistry Institute)
SUMITTED: O8Feb63 DATE ACQ: 3lMar64 ENCL: 00
SUB CODE: GC, GP NO REF SOV: 001 OrHER: 000
Card'

ACCESSION NR: AP4033409 S/0076/64/038/003/0742/0745
AUTHORS: Smirnova, V.I.; Zhuravlevas G.S.,; Yanoval K.Gs; Shigorins
D.N,
TITLE: Electron paramagnetic resonance study ok the structure and
behavior of radicals formed on y-l,,R -, and photolytic irradi-
ation of acetaldehyde and formaldehyde
SOURCE: Zhurnal fizicheskoy khimiij v. 38, no. 3, 1964, 742-745
TOPIC TAGS: electron paramagnetic resonances fred;radical, acetalde-I
jiyde, formaldehyde,-beta irradiation, gamma irradiationp ultreoriolet,
i irradiation
ABSTRACT: The structure and behavior of free radicals formed up*
on I
and ultraviolet irradiation of acetaldehyde and upon(3- and
f7 irradiation of formaldehyde were studied by the electron para-
agnetic resonance (EPR) method. The studied compounds were conden-I
M
sed from the gaseous phase into special ampules and were irradiated
at -190C. Upon irradiation of acetaldehyde with)s-ray doses of 3
million rads, a singlet is obtained, which is attributed to the
Card
113

ACCESSION NR: AP4033409
breakage of the C-C bond and formation of CH and CHO radicals,
where CH radicals rapidly recombine but CH63radical has a localized.
3
unpaired*electron and consequently it does not possess nuclear
magnetic moment. At do ses of 40 to-100 million rads a triplet
with 2 additional less intense lines-is observed and is attributed
to the supposition of the singlet and quartet 4btained at dos e.,s of
3 million rads. The line width was AH = 47.0 oersted. Upon increase
of the temperature from -130 to -120C the singlet disappears and
the quartet becomes symmetrical. It was assumed that the quartet
appears upon the breakage of C-H bond with the formation of CH3-C - 0
radicals or upon the breqkage of the C-0 bond in the polymeric chaini
with the formation of O-C -0 radical. The quenching temperature
of the quartet was -105 to'-50C. OnA-irradiation of formaldehyde
.at doses of 7 million radsthe doublet formed is related to the for-
mation of -0-CH-0- type radical. At doses of 70 million rads the
spectrum appears as an assymetrical line with-shoulders which may be!
composite of two different spectra of the -0-CH-0- (doublet) and
card 2/3
A

ACCESSION NR: AP4033409
_C11- O-C11 radicals (triplet). At 7 million rad dose side signals
had2a sep3ration of 125 oersted with the central doublet of 13 oer-
sted between its components. Beta irradiation of polyformaldehyde
produces a triplet which is attributed to CH 0 or CH -0 CH
13 f m2
radicals. It was concluded that the natur; oFradica _0 ed on
irradication of acetaldehyde does not depend on the aggregate state
of the compound and that the temperature of radical quenching
apparently depends on the aggregate state of the acetaldehyde mono-
mer. Orig. art. has: 4 figures
SSOCIATION:.Nauchno-issledovatelfskiy fiziko-khimicheskiy institut
(Scientific Researph Institute of Physical Chemistry)
SUBMITTED: 14Mar63 ENCL: 00
i. SUB CODE NR REF SOV: 004 OTHER: 002
Card 313

SIVONOV@ A.P.--l SHIGORIN, D,N.
I - I : @.m. - @ C, .. @ @-
lnfri@@. ab---Drption spect-ram and structure of crystalline
lithYmai-methylate. Op'L. i speku,r. 17 no.6:848-858 D 164.
(MIRA 18:3)

-ja
.1 r CYI- LeS I.,
18 Pig
-!,s t, tu L iffier-

L 16195-65.
ACCESSION NR: AP4046084
Photo- illuminated powders under 'Vacuum@:at -77K ave-no EPR-s1gna_L_:-Ln
9 samp e9,i-_-:.@.-..-.-y
crystallized from ethanol andIn luifiln'ophor systehia-M. H-O- R 4 singlet
appeared whose intensity increased prop-drtionallylio the IntenIsity.of illumina-Mon.-
Photoactivation of systems with the luminescent chromophore ,C=O gave a sing-@
let and EPR spectra corresponding to radicals of the solvent. Photoactivation'oU
systems containing the chromophoric atom iW,: gave a weak singl6t and *intense-
spectra of the solvent radical (radical yf6ld, 1n n 2). If the -N. atom which
formed a H-bond with the 0-H groups did riot affect the eliec,tr6n' excitation, the
radical yield was small. In solvents .(hydrocarbons) which did- not. contaih the7 jt4R,
group capable of forming H-@bohils-,Ahe opl@o@es c1id'no,Cg'iv'iEk noticeable EPR.4
signals. It was concluded the H-bond played impojztant role in the process--of , f,
'forming radicals from a matrix as a, result of.deactivating activated states of.-
1molecule. This is a two- stage process (se'erenclosed figure). Formation of:the
I radical complex takes place in the firsit-s-tage as a res of the transition* of'the
Ult
H atom from the molecule of the matrix-to the e
luminophor molecule due to abm.
sorption of a quantum of light in transitions. The radical complex is
decomposed in the second stage.forming rafficals of the matrix--clue to absorption
qard 2/4
L

PISKUNOV, A.K.; KHOLMOGOROV, V.Ye.; SHIGORINI.,,.D.N.; VEREYN, N.V.;
OZEROVA, G.A.
Mechanism underlying the formation of radicals during
photoirradiation of triphenylamine ethanol solutions frozen
at 770 K. DokL AN SSSR 154 no-4:910-913 F 164.
(MIRA 17:3)
1. Fiziko-khimicheskiy institut, im. L.Ya. Karpova. Predstav-
leno akademikom A.N. Tereninym.

ACCESSION NR: AP4040960 S/002-0/64/156/005/3-174/1177
AUTHOR: Urentlyev, A. P.; Panova, r.. V.; Shigo a, D. K.;
A Rukhadze, Ye*'G*
TITLE: EPR spectra@of optically4otive oh.e'late compoupds of copper with
oxyaldimines and oxyketimines
SOURCE: AN SSSR. Ilok:Lady*,, v. 1561 noe 5, 1964$ 1174-1177
!TOPIC TAGS: EFR, EPR spectrum, cheldte compound,, optically-active chelate
compound, copper, copper compound, copper-chelate compound,, aldimine compound,
I
ketimine compound, copper-oxyaldimine compound, copper-oxykatimine compound'
AMTRACT: It is a well-known fact-that the degree of delocalization of an-unpaired
ielectron can be studied directly by the electron)-paramagnetic resondbee method,.
14ence, one and the same structural peculiarities of molecules can be found in
:the optical activity and EPR spectra. With this in mind, the autbors studied.
Ithe EPR spectra of the titled chelate compounds of copper. The analysis was
@carried out an a superheterodyne EPR spectrometer with a frequency of 9455 Mae
'All of the compounds in a chloroform solution produce EER spectra which are
charactertzed by four lines of a superfine stru#ureq which orlZinate as the
result of the.interaotion of the.copper atom's n@olear moment (1,@e '@/2) with the
Ca,d