A conformational study of aromatic imide compounds. Part 2. Compounds containing diphenyl sulfide, diphenyl sulfone, and diphenylmethane moieties

Article abstract of DOI:10.1016/S0022-2860(01)00709-8

An attempt was made to estimate the dihedral angles, φ, ψ, ω₁, and ω₂, of bis(4-hydroxyphthalimide)s (BHPI) and bis(phenylphthalimide)s (BPI) having diphenyl sulfide, diphenyl sulfone, or diphenylmethane linkages at the center of mol

Full text of DOI:10.1016/S0022-2860(01)00709-8

Journal of Molecular Structure 602±603 )2002) 417±428
www.elsevier.com/locate/molstruc
A conformational study of aromatic imide compounds. Part 2.
Compounds containing diphenyl sul®de, diphenyl sulfone, and
diphenylmethane moietiesq
*
Keitaro Aimi, Akira Yamane, Shinji Ando
Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8552, Japan
Received 21 March 2001; accepted 4 April 2001
Abstract
An attempt was made to estimate the dihedral angles, f, c, v1, and v2, of bis)4-hydroxyphthalimide)s )BHPI) and
bis)phenylphthalimide)s )BPI) having diphenyl sul®de, diphenyl sulfone, or diphenylmethane linkages at the center of mole-
cules using solid±state 13C CP/MAS NMRand ab initio nuclear shielding calculations. The TOSS and TOSS & DD pulse
sequences were performed in the NMRmeasurements to obtain exact chemical shifts of each carbon. Total energies were
calculated using the B3LYP/6-31G)d) level of theory, and shielding constants were calculated using the RHF/6-31G)d) level of
theory for diphenyl sul®de, diphenyl sulfone, diphenylmethane with varying angles of f, c from 0 to 1808 at intervals of 108. It
was clari®ed that the ±S± and ±SO2± linkages lead asymmetrical conformations with different v1 and v2 or with different f
and c for BHPIs and BPIs. In contrast, the compounds having ±CH2± linkages have symmetrical conformations. The dihedral
angle of imide ring and phenylene ring )v) are in the range of 40±908, and the dihedral angles ꢀf; c† distribute in the stable
regions of the energy surfaces ranging from 40 to 908. q 2002 Elsevier Science B.V. All rights reserved.
Keywords: CP/MAS NMR; Shielding constant; Dihedral angle; Diphenyl structure; Polyimide
1. Introduction
mined by the relationship between the two dihedral
angles, f and c. That is to say, when the signal of a
certain carbon is singlet, two dihedral angles f and c
are identical, otherwise, they are different. Moreover,
dihedral angles can be estimated by comparing 13C
NMRchemical shift differences between phenyl
carbons with variations in calculated nuclear shield-
ings. For all the compounds we studied, the dihedral
angles at diphenyl linkages were estimated as f ˆ c;
and the dihedral angles distributes in the stable
regions of the energy surfaces ranging from 30 to
908. In addition, the dihedral angle v ranges between
45 and 908. In this article, we estimate the conforma-
tions of the BHPIs and BPIs that have diphenyl sul®de
)DPS), diphenyl sulfone )DPSO2), diphenylmethane
In Part 1 of this series [1], we have estimated the
dihedral angles of BHPIs, BPIs, and ODPA/ODA
polyimide that have diphenyl ether )DPO) and benzo-
phenone )DPCO) linkages at the center of molecules
or in the repeating unit. From the results of shielding
constant calculations, it was clari®ed that the number
of peaks of the carbons in diphenyl region is deter-
q
Dedicated to Professor Graham A. Webb on the occasion of his
65th birthday.
* Corresponding author. Tel.: 181-3-5734-2137; fax: 181-3-
5734-2889.
E-mail address: sando@polymer.titech.ac.jp )S. Ando).
0022-2860/02/$ - see front matter q 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-2860)01)00709-8

418
K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
methylidenediphenylene)-bis-)2-phenyl-isoindole-
1,3-dione) )BPI-DPCH2)), which have the same
skeletal structures as those of BHPI but no
hydroxyl groups, were also synthesized
As an example, the synthesis of BHPI-DPS is
described as follows: a mixture containing 15.2 g of
N-methyl-2-pyrrolidinone )NMP) and 7.6 g of o-
xylene was added to 3.79 g )23.12 mmol) of 4-hydro-
xyphthalic anhydride and 2.50 g )11.56 mmol) of
4,40-diaminodiphenyl sul®de. This mixture was then
heated under re¯ux at 1908C for several hours to
remove the water of reaction by azeotropic distilla-
tion. The mixture was allowed to stand at room
temperature and poured into methanol. The solid
product was ®ltered out and rinsed with acetone,
and dried in a vacuum at 1008C for 6 h. The obtained
BHPI-DPS was 5.35 g )91.0% yield). BPIs were
synthesized in the same manner except for using
phthalic anhydride instead of 4-hydroxyphthalic
anhydride. BHPI-DPS and BHPI-DPCH2 were recrys-
talized from tetrahydrofuran )THF), and BHPI-
DPSO2 was recrystalized from acetone. All BPI
samples were recrystalized from chloroform.
Scheme 1.
)DPCH2) linkages at the center of molecules. These
diphenyl linkages frequently appear in high-perfor-
mance engineering plastics.
2.2. NMR measurements
Solution state 13C NMRspectra were observed with
JEOL GSX-500 spectrometer operating at 125 MHz.
Dimethylsulfoxide )DMSO-d6) was used as a solvent
for BHPIs, and chloroform-d was used for BPIs. The
DEPT sequence was used for selective observation of
protonated carbons. Tetramethylsilane )TMS) was
used as the internal standard ꢀdC ˆ 0 ppm†:
2. Experimental
2.1. Synthesis
The general formula of BHPI and BPI are
shown in Scheme 1. Two BHPIs that have central
linkages of ±SO2± )N,N0-)4,40-sulfonyldipheny-
lene)-bis-)5-hydroxy-2-phenyl-isoindole-1,3-dione),
BHPI-DPSO2) and ±CH2± )N,N0-)4,40-methylidene-
diphenylene)-bis-)5-hydroxy-2-phenyl-isoindole-1,3-
dione), BHPI-DPCH2) were provided by NTT
corporation. N,N0-)4,40-sulfanyldiphenylene)-bis-)5-
hydroxy-2-phenyl-isoindole-1,3-dione) )BHPI-DPS)
that has the central linkage of ±S± was synthesized
according to the literature [2]. In order to exclude the
effect of intermolecular hydrogen bonding, three
bisphenylenephthalimide )N,N0-)4,40-sulfanyldiphe-
nyle0ne)-bis-)2-phenyl-isoindole-1,3-dione) )BPI-DPS),
N,N -)4,40-sulfonyldiphenylene)-bis-)2-phenyl-isoin-
dole-1,3-dione) )BPI-DPSO2), and N,N0-)4,40-
Solid-state 13C CP/MAS NMRspectra were
observed with JEOL GSX-270 spectrometer operating
at 67.8 MHz. The total suppression of spinning side-
band )TOSS) pulse sequence was used to suppress
spinning sidebands. The pulse sequence that combines
TOSS and the dipolar dephasing )non-quaternary
carbon suppression) )TOSS & DD) was also used
for selective observation of the non-protonated
carbons. The CP contact time was 2 ms, and the
recycle delay was 5 s. The chemical shifts calibrated
indirectly through the adamantane peak observed at
lower frequency )29.5 ppm relative to TMS).
2.3. MO calculations
As mentioned in Part 1, the B3LYP/6-31G)d) level

K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
419
Fig. 1. Conformational energy surface of diphenyl sul®de )DPS)
calculated using B3LYP/6-31G)d) level of theory. The dihedral
angles of diphenyl sul®de structures reported for single crystals
are plotted by ®lled circles within the range of 08 # f # 908 and
c $ f )see text).
Fig. 3. Conformational energy surface of diphenylmethane
)DPCH2) calculated using B3LYP/6-31G)d) level of theory. The
dihedral angles of diphenylmethane structures reported for single
crystals are plotted in the same manner as in Fig. 1.
of theory was used for the calculation of conforma-
tional energies, and the RHF/6-31G)d) level of theory
was used for the shielding constant calculations. The
program package of molecular orbital theory used was
gaussian 98 installed in the Computer Center of
Tokyo Institute of Technology [3]. Two dihedral
angles, f and c )refer to Scheme 2 of Part 1) of
diphenyl sul®de )DPS), diphenyl sulfone )DPSO2),
and diphenylmethane )DPCH2) were varied from 0
to 1808 at 108 intervals. Geometrical parameters
)bond lengths and bond angles) were optimized for
each conformation, followed by 13C magnetic
shielding calculation using GIAO-CHF method [4].
3. Results and discussion
3.1. Conformational energy surfaces
Figs. 1±3 show the conformation energy surfaces
of DPS, DPSO2 and DPCH2, respectively. The inter-
vals of lines in the energy contour maps are 1 kJ/mol
in Figs. 1 and 3, and 2 kJ/mol in Fig. 2. Since the left
and right halves of the energy surface are point-
symmetrical with respect to the point of )908,908),
we consider only the left half. The dihedral angles
of diphenyl sul®de [5±22], diphenyl sulfone [23±
41], and diphenylmethane [42±63] structures reported
for single crystals are also plotted in Figs. 1±3. These
data were collected from the Cambridge Structural
Fig. 2. Conformational energy surface of diphenyl sulfone )DPSO2)
calculated using B3LYP/6-31G)d) level of theory. The dihedral
angles of diphenyl sulfone structures reported for single crystals
are plotted in the same manner as in Fig. 1.

420
K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
Database [64]. Since the benzene rings in DPO and
DPCO have symmetrical structures, the conformation
of ꢀf; c† is in principle same as that of ꢀc; f†: Hence,
the conformations of single crystals are plotted in the
area of f , c:
)608,608) and )1208,1208), can pass both the transition
states of )08,908) or )908,908). Straûner has reported
conformational energy surfaces of DPCH2 using AM1
methods and B3LYP/3-21G)d) level of theory [68].
According to his report, the energy minimum of
DPCH2 is located at )578,578), and it agrees with the
high-level Hartree±Fock ab initio calculation )MP2)
of 58.58 [69]. The shapes of the surfaces reported )HF/
6-31G)d) [69] and B3LYP/3-21G)d) [68]) are almost
identical to that of Fig. 3. The dihedral angles of
single crystals having diphenylmethane linkages are
located close to the minimum region and tend to
distribute on the line of f ˆ c )Case A) or f 1 c ˆ
908 )Case B).
The energy minima are found at ꢀf; c† ˆ ꢀ308; 608†
and )608,308) for DPS )Fig. 1). The large minimum
region ),1 kJ/mol) extends from )08,908) to )908,08).
The energy difference between the minimum point
and )08,908) is 0.44 kJ/mol. This value is slightly
smaller than that for DPO )0.67 kJ/mol, see Part 1).
Hence, the transition accompanying the rotation of
benzene rings between the two minimum points, i.e.
)308,608) to )1508,1208), in which both are mutual
enantiomers, passes the conformation of )08,908). On
the other hand, the energy difference between the
minimum point and )908,908) is 5.33 kJ/mol, which
is much smaller than that of DPO )17.07 kJ/mol).
Anwer et al. has reported a conformational energy
surface and the energy minimum at )408,408) for
DPS using MM2 calculation [65]. The overall surface
shape obtained from MM2 is similar to that of Fig. 1.
The energy minimum was reported as ꢀf; c† ˆ
ꢀ358; 358† for DPS from a semi-empirical )AM1)
calculation [66]. These stable conformations also
agree well with our results. Most of the dihedral
angles of the single crystals having diphenyl sulfanyl
linkages are located close to the minimum region and
tend to distribute on the line of f ˆ c )Case A) or
f 1 c ˆ 908 )Case B).
3.2. Shielding constant calculation
The surface shapes of the shielding constants for
DPO was examined in Part 1 [1]. It was clari®ed
that the shielding constants of diphenyl carbons
signi®cantly vary with the dihedral angles f and c.
In the case of f ˆ c )Case A), the shielding constants
of symmetrical two carbons in different phenyl rings
0
)Cx and Cx ) are identical, otherwise, they are
different. Hence, the conformation of diphenyl region
can be inferred from the number of peaks in NMR
spectrum. Although the nuclear shieldings of all
carbons show dihedral angle dependence, we selected
the chemical shifts of C4 and C6 for estimating the
dihedral angles from the reasons stated in the
preceding paper [1].
The energy minimum is found at )908,908) for
DPSO2 )Fig. 2), which agrees with those of MM2
calculation [65] and HF/3-21G level of theory [67].
The minimum region ),2 kJ/mol) extends from
)708,708) to )1108,1108). The energy difference
between the minimum point and )08,908) is 11.84 kJ/
mol, which indicates that the energy barrier for the
benzene ring rotation is very high for DPSO2
compared to other diphenyl structures. Most of the
dihedral angles of single crystals having diphenyl
sulfone linkages are located in the minimum region.
The energy minimum is found at )608,608) for
DPCH2 )Fig. 3). The minimum region ),1 kJ/mol)
ranges within 108 of )608,608). The energy difference
between the minimum point and )08,908) is 3.13 kJ/
mol, and that of )908,908) is 2.54 kJ/mol. This indi-
cates that the transition accompanying the rotation of
benzene rings between the two energy minima, i.e.
Figs. 4±6 show the dihedral angle dependence of
shielding constants of C4 and C6 for DPS, DPSO2 and
DPCH2, respectively. In Case A, the shielding
constants of C4, C6 and their difference )D4,6) signi®-
cantly vary with the dihedral angles, and the dihedral
angles can be estimated from the curve of D4,6. On the
0
0
other hand, the difference between C4 and C5 )D4,4
)
was used for the estimation of dihedral angles in Case
B because the dihedral angle dependence of D4,6 for
DPS )Fig. 4b) and DPCH2 )Fig. 6b) is very small.
3.3. Shielding constant calculation of NPPI
The dihedral angles v is de®ned by the interring
rotation of the imide ring and phenylene ring in BHPIs
and BPIs. The chemical shifts of diphenyl carbons, C1,
C2, C3, and C5 should be in¯uenced by the dihedral
angles v1 and v2. The chemical shifts of C4 and C6 are

K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
421
Fig. 4. Dihedral angles dependence of the shielding constants of
diphenyl sul®de )DPS) for the cases of )a) f ˆ c )Case A) ꢀ08 #
f # 908†; and )b) f 1 c ˆ 908 )Case B). The shielding constant
difference between C4 )s4) and C6 )s6) is expressed as D4,6, and that
Fig. 5. Dihedral angle dependence of the shielding constants of
diphenyl sulfone )DPSO2) for )a) Case A and )b) Case B. The
plots are in the same manner as in Fig. 4.
between C4 )s4) and C0 )s4 ) is expressed as D4,4
0
0
.
4
constant of C1 shows a considerable decrease as the v
increases, whereas that of C4 is insensitive to the
variation of v. The shielding constant of C2 increases
as the v increases from 0 to 508, and that of C5 gently
decreases as the v increases. These results indicate
that when the dihedral angles at imide-phenyl bonds
)v1 and v2) of BHPI and BPI are different, two
symmetrical carbons in different phenyl rings exhibit
different chemical shifts. For example, when v1 is 408
and v2 is 908, a displacement of ca. 6 ppm could be
insensitive to the dihedral angle v because they are
located at the meta-positions. The shielding constants
of N-phenylphthalimide )NPPI) were calculated to
investigate the dihedral angle )v) dependence of
nuclear shieldings of such diphenyl carbons. The
geometry of NPPI was optimized using B3LYP/6-
31G)d) level of theory with varying v at 108 intervals,
and the shielding constants were calculated using
RHF/6-31G)d) level of theory.
0
observed for the chemical shifts of C1 and C1 : Conse-
Fig. 7 shows the v dependence of the shielding
constants of phenyl carbons in NPPI. The shielding
quently, even if the dihedral angles f and c take the
same value, two split peaks can be observed for C1,

422
K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
Fig. 7. Dihedral angle )v) dependence of the shielding constants of
phenyl carbons of N-phenylphthalimide. The numbers of carbons
correspond to those in Scheme 1.
Fig. 6. Dihedral angle dependence of the shielding constants of
diphenylmethane )DPCH2) for )a) Case A and )b) Case B. The
plots are in the same manner as in Fig. 4.
C2, C3, and C5 when two dihedral angles v1 and v2 are
different.
3.4. Estimation of dihedral angles
Dihedral angle v can be estimated using the corre-
lation between the chemical shift difference of solid-
state and solution-state chemical shifts )Dsolid±solution
)
for C1 carbon and the dihedral angles determined by
X-ray crystallography [70]. The dihedral angle v can
be estimated by applying a value of Dsolid±solution for the
correlation curve in Fig. 7 of Part 1.
Fig. 8. )a) Solution, )b) TOSS, )c) TOSS & DD and )d) subtracted )c
from b) NMRspectra and signal assignments of BHPI-DPS.
Symbols in the spectra correspond to the carbons shown in Scheme
1.
Figs. 8±13 show the 13C solution-state NMRand

K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
423
Fig. 9. )a) Solution, )b) TOSS, )c) TOSS & DD and )d) subtracted )c
from b) NMRspectra and signal assignments of BHPI-DPSO 2.
Fig. 10. )a) Solution, )b) TOSS, )c) TOSS & DD and )d) subtracted
)c from b) NMRspectra and signal assignments of BHPI-DPCH 2.
solid-state CP/MAS NMRspectra of BHPI-DPS,
BHPI-DPSO2, BHPI-DPCH2, BPI-DPS, BPI-DPSO2
and BPI-DPCH2, respectively, together with their
signal assignments. The peaks of solution-state
NMRspectra were assigned using the substituent
shielding effects on benzene and related compounds
[71]. The peaks of solid-state NMRspectra were
assigned by referring to the assignment of solution-
state spectra. The peak positions expected from the
shielding constant calculations were also used to
assign the signals in diphenyl region. The dihedral
angles, v1, v2, f and c of each sample are estimated
in the following.
and C5. Split peaks are also observed for the other
diphenyl carbons in subtracted spectrum )Fig. 8d).
Considering the number of peaks in Fig. 8, BHPI-
DPS should have an asymmetric conformation, in
which the values of f and c are different. The plots
of single crystal structures in Fig. 1 show that most of
the asymmetric DPS structures have nearly Case B
structures ꢀf 1 c ˆ 908†: Hence, we assumed that
f 1 c ˆ 908 for BHPI-DPS. The signals in the
TOSS spectrum )Fig. 8b) are overlapped with each
other, but the peaks at 126.2, 127.9, 127.9 and
0
0
129.5 ppm are assigned to C1, C3, C1 and C3 , respec-
tively, from the peak ®tting using Lorentzian func-
tions )the ®tted spectrum is not shown).
Furthermore, the average chemical shifts of C1 and
3.4.1. BHPI-DPS
For symmetrical molecular conformations with the
same f and c and the same v1 and v2, the signals of
carbons located at symmetrical positions in the phenyl
0
0
0
0
C3 )d1,3.solid) and C1 and C3 )d1 ,3 .solid) were used for
the estimation of the dihedral angle v. The
D1,3.solid±solution value of 20.9 ppm corresponds to v ˆ
0
rings of BHPI and BPI )Cx and Cx ) should be singlet
0
0
55 ^ 58; and the D1 ,3 .solid±solution value of 0.7 ppm
corresponds to v ˆ 70 ^ 58: From the subtracted
as mentioned above. In the TOSS & DD spectrum of
BHPI-DPS )Fig. 8c), split peaks are observed for C2

424
K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
Fig. 11. )a) Solution, )b) TOSS, )c) TOSS & DD and )d) subtracted
)c from b) NMRspectra and signal assignments of BPI-DPS.
Fig. 12. )a) Solution, )b) TOSS, )c) TOSS & DD and )d) subtracted
)c from b) NMRspectra and signal assignments of BPI-DPSO 2.
spectrum of Fig. 8d, the chemical shift difference
between C4 )135.3 ppm) and C0 )132.8 ppm) was
are overlapped with each other, and the value of D4,6 is
estimated to be smaller than 1 ppm, which indicates
that the dihedral angles f and c are larger than 608 by
applying this value to Fig. 5a.
4
0
estimated as D4;4 ˆ 2:5 ppm: By applying this value
to the curve in Fig. 4b, the dihedral angles are esti-
mated as ꢀf; c† ˆ ꢀ40 ^ 58; 50 ^ 58†:
3.4.3. BHPI-DPCH2
3.4.2. BHPI-DPSO2
Single peaks are observed for C2 and C5 in the
TOSS & DD spectrum )Fig. 10c). The other diphenyl
carbons also show single peaks in the subtracted spec-
trum )Fig. 10d). These results indicate that the dihe-
dral angles of f and c are identical for BHPI-DPCH2.
The solution-state chemical shift of C1 is 127.1 ppm
)Fig. 10a), and the solid-state chemical shift of C1 and
C3 is 124.9 ppm )Fig. 10d). The value of D1,3.solid±solution
)22.2 ppm) thus obtained corresponds to v ˆ 40 ^
58: Since only one peak is observed for C4 and C6 at
132.3 ppm, the dihedral angles of f and c are esti-
mated as ꢀf; c† ˆ ꢀ45 ^ 58; 45 ^ 58† or ꢀ90 ^
58; 90 ^ 58† by applying the value of D4,6 )0 ppm)
to Fig. 6a. In the calculated energy surface of
DPCH2 )Fig. 3), both structures are possible.
Single peaks observed for C2 or C5 in the TOSS &
DD spectrum )Fig. 9c) indicates that the dihedral
angles of f and c are identical for BHPI-DPSO2. In
addition, since only single broad peak of C1, C3, C4
and C6 is observed in the subtracted spectrum )Fig.
9d), the dihedral angles v1 and v2 are also estimated
to be identical. The peak splittings observed for Ca
and Cf should originate from intermolecular interac-
tion such as molecular packing effect because these
carbons are insensitive to the conformational change.
The value of Dsolid±solution was estimated as 1.4 ppm
from dsolid ˆ 129:4 ppm and dsolution ˆ 128:0 ppm in
Fig. 9a and d. Hence, the dihedral angle v is estimated
as 90 ^ 58: On the other hand, the signals of C4 and C6

K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
425
DPSO2 should have an asymmetric structure.
Although splittings of peaks are observed for C2 and
C5 in Fig. 12c, the calculated shielding constants of
the diphenyl carbons are inconsistent with Case B
taking account of the peak positions in NMRspectra.
Hence, we assumed that these splittings originate not
from the difference in f and c, but from the differ-
ence in v1 and v2. As shown in Fig. 7, when the range
of v is limited between 40 and 908, a maximum
displacement of 3 ppm to lower frequency can be
induced for C5 by the difference in v, but a displace-
ment of less than 1 ppm can be induced for C2. The
spectral shapes of C2 and C5 observed in the TOSS &
DD spectrum of Fig. 12c agree with this calculation:
two split peaks are observed for C5, whereas one
broad peak is observed for C2.
The chemical shift of C1 in solution )dsolution) is
126.3 ppm. Two dihedral angles v1 and v2 were esti-
mated from the difference between dsolution and d1,3.solid
0
0
)124.1 ppm) and that between dsolution and d1 ,3 .solid
)128.5 ppm). The D1,3.solid±solution values of 22.2 and
12.2 ppm correspond to v1 ˆ 50 ^ 58; and v2 ˆ
90 ^ 58; respectively.
The dihedral angles f and c are estimated to be
larger than 608 by applying the value of D4,6 )less than
1 ppm) to Fig. 5a. Considering the chemical shift
Fig. 13. )a) Solution, )b) TOSS, )c) TOSS & DD and )d) subtracted
)c from b) NMRspectra and signal assignments of BPI-DPCH 2.
0
0
difference between C5 and C5 )D5,5 ), the f and c
are limited to the region around )908,908). When the
dihedral angles, v1, and v2, are 50 and 908 as esti-
3.4.4. BPI-DPS
Split peaks are observed for C2 and C5 in the
TOSS & DD spectrum )Fig. 11c), and split peaks
are also observed for the other diphenyl carbons in
the subtracted spectrum )Fig. 11d). Considering
the number of peaks in Fig. 11, BPI-DPS should
have an asymmetric structure. The chemical shift
of C1 in solution is 126.8 ppm in Fig. 11a, and the
0
mated above, the value of D5,5 could be 2 ppm in Fig.
7. This agrees well with the experimental difference
between C5 )141.5 ppm) and C0 )139.8 ppm).
5
3.4.6. BPI-DPCH2
The dihedral angles, f and c are estimated to be
identical because singlet peaks are observed for
diphenyl carbons of BPI-DPCH2 as seen in Fig. 13c
and d. The Dsolid±solution value of 22.5 ppm, which is
obtained from the solution-state and solid-state
chemical shift of C1 )126.4 and 123.9 ppm) corre-
sponds to v ˆ 45 ^ 58: The dihedral angle f and c
are estimated as ꢀf; c† ˆ ꢀ58 ^ 58; 58 ^ 58† by
applying the value of D4,6 )1.2 ppm) to Fig. 6a.
Table 1 summarizes the dihedral angles, v, f and
c, thus estimated above. Comparing the estimated
values of f and c with the conformational energy
surfaces, ꢀf; c† ˆ ꢀ408; 508† of BHPI-DPS and
)388,528) of BPI-DPS are located in the most stable
0
solid-state chemical shift of C1 and C1 are
127.9 ppm and 123.5 ppm, respectively. The
values of D1,3.solid±solution )23.3 and 1.5 ppm) thus
obtained correspond to v1 ˆ 40 ^ 58 and v2 ˆ
0
75 ^ 58: Furthermore, the D4,4 value of 4.1 ppm
is obtained from the subtracted spectrum )Fig.
11d). The dihedral angles of f and c are esti-
mated as ꢀf; c† ˆ ꢀ38 ^ 58; 52 ^ 58† by applying
0
the value of D4,4 to Fig. 4b.
3.4.5. BPI-DPSO2
The split peaks for C5 )Fig. 12c) and protonated
diphenyl carbons )Fig. 12d) indicate that BPI-

426
K. Aimi et al. / Journal of Molecular Structure 602±603 02002) 417±428
Table 1
Estimated dihedral angles v, f and c, and relations between two
dihedral angles f and c.
rings )v) is between 40 and 908, and the dihedral
angles ꢀf; c† distribute in the stable regions of the
energy surfaces ranging from 40 to 908.
Sample
Casea v )8)
ꢀf; c† )8)
BHPI DPS
B
A
A
55 ^ 5; 70 ^ 5 ꢀ40 ^ 5; 50 ^ 5†
DPSO2
90 ^ 5
40 ^ 5
60±90
Acknowledgements
DPCH2
ꢀ45 ^ 5; 45 ^ 5† or
ꢀ90 ^ 5; 90 ^ 5†
We wish to thank S. Sasaki and T. Matsuura at NTT
for providing 4-hydroxyphthalimide and bis)4-
hydroxyphthalimide)s.
BPI
DPS
DPSO2
DPCH2
B
A
A
40 ^ 5; 75 ^ 5 ꢀ38 ^ 5; 52 ^ 5†
50 ^ 5; 90 ^ 5 ꢀ90 ^ 5; 90 ^ 5†
45 ^ 5
ꢀ58 ^ 5; 58 ^ 5†
a
In case A, f ˆ c; and in case B, f 1 c ˆ 908:
region of DPS )Fig. 1). Furthermore, the estimated
conformations of f ˆ c . 608 for BHPI-DPSO2 and
ꢀf; c† ˆ ꢀ908; 908† for BPI-DPSO2 are located in the
stable conformation of DPSO2. The estimated confor-
mation of )58, 58) for BPI-DPCH2 is also located in
the most stable region of DPCH2 )Fig. 3). Although
we cannot choose unique conformation of BHPI-
DPCH2, two possible conformations ))458,458) and
)908,908)) are located in the slightly unstable regions
)about 3 kJ/mol higher than the energy minimum).
The examination of the conformations stated above
clearly shows that the introduction of ±S± and ±
SO2± linkages to the center of molecules lead to
asymmetrical conformations of BHPI and BPI,
while the introduction of ±CH2± linkages provides
symmetric conformations.
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