Syntheses and quadratic nonlinear optical properties of 2,7-fluorenylene- and 1,4-phenylene-functionalized: O -carboranes

Article abstract of DOI:10.1039/c9dt02645b

o-Carboranes C-functionalized by (4-substituted-phen-1-yl)ethynyl-1,4-phenyl groups or (2-substituted-fluoren-7-yl)ethynyl-2,7-fluorenyl groups, in which the pendant functionalization is electron-withdrawing nitro or electron-donating diphenylamino groups

Full text of DOI:10.1039/c9dt02645b

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DOI: 10.1039/C9DT02645B
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ARTICLE
Syntheses and Quadratic Nonlinear Optical Properties of 2,7-
Fluorenylene- and 1,4-Phenylene-Functionalized o-Carboranes
Peng Jiang,a Zhaojin Wang,a,b Graeme J. Moxey,c Mahbod Morshedi,c Adam Barlow,c Genmiao
Received 00th January 20xx,
Accepted 00th January 20xx
Wang,c Cristóbal Quintana,c Chi Zhang,a,d Marie P. Cifuentesa,c and Mark G. Humphreya,c,*
DOI: 10.1039/x0xx00000x
o-Carboranes C-functionalized by (4-substituted-phen-1-yl)ethynyl-1,4-phenyl groups or (2-substituted-fluoren-7-
yl)ethynyl-2,7-fluorenyl groups, in which the pendant functionalization is electron-withdrawing nitro or electron-donating
diphenylamino groups, have been synthesized and in many cases structurally characterized. Diphenylamino-containing
examples coupled via the two p-delocalizable bridges to the electron-accepting o-carborane unit exhibit the greater
quadratic optical nonlinearities at 1064 nm (hyper-Rayleigh scattering, ns pulses), the nonlinearities also increasing on
proceeding from 1,4-phenylene- to 2,7-fluorenylene-containing bridge. The most NLO-efficient example 2-(n-butyl)-1-(2-
((9,9-di(n-butyl)-2-(N,N-diphenylamino)-9H-fluoren-7-yl)ethynyl)-9,9-di(n-butyl)-9H-fluoren-7-yl)-1,2-ortho-carborane,
consisting of diphenylamino donor, fluorenyl-containing bridge, o-carborane acceptor, and solubilizing n-butyl units, exhibits
large <b>HRS (230 x 10-30 esu) and frequency-independent (two-level model) <b0> (96 x 10-30 esu) values. Coupling two 2-
((9,9-di(n-butyl)-2-(N,N-diphenylamino)-9H-fluoren-7-yl)ethynyl)-9,9-di(n-butyl)-9H-fluoren-7-yl) units to the 1,2-ortho-
carborane core affords a di-C-functionalized compound with enhanced nonlinearities (309 x 10-30 esu and 129 x 10-30 esu,
respectively).
www.rsc.org/
phenyleneethynylene-based,22-29 phenylenevinylene-based,5,
Introduction
30-34
and other π-bridges,24, 35-38 which has afforded a large
Icosahedral closo-carboranes have attracted considerable
attention as emitting1-8 and electronic materials,9-13 as well as
for applications in two-photon absorption,14-16 due to their
electron-withdrawing properties and their three-dimensional
electron delocalization. ortho-Carborane (o-Cb) is an efficient
electron-acceptor comparable in strength to the
tetrafluorophenyl group,17, 18 and therefore has potential in
number of NLO-efficient examples, and thereby facilitated the
development of design rules for the optimization of NLO
performance. One observation is that the quadratic NLO
coefficient β generally increases with π-bridge lengthening in
31, 36, 39-41
such compounds,30,
but the solubilities of the
compounds usually decrease upon increasing the length of the
bridge. Bridge substitution with alkyl groups has been employed
to mitigate this problem,28, 31, 41-44 but these solubilizing groups
are usually located in the π-bridge plane, and are therefore
inefficient at suppressing the aggregation that results in
decreasing solubility.
In the present work, we have pursued possible improvement
in the NLO performance of D-B-A compounds by employing o-
Cb as acceptor and exploring p-bridge modifications to permit
donor-p-bridge-acceptor (D-B-A) assemblies of interest in
nonlinear optics, but the quadratic nonlinear optical (NLO)
performance of Cb dyads has thus far remained modest, and
few efficient examples are extant.19-21
In contrast to the dearth of studies with o-Cb-based
compounds, there has been considerable success in
synthesizing quadratic NLO-active D-B-A compounds with
organic and inorganic donor and acceptor groups and
incorporation of out-of-plane solubilizing groups. Carboranes
possess two active CH sites rendering derivatization (and
therefore access to the targets) a facile process. We have
targeted π-bridge elongation with fluorenyl units because the
plane of the alkyl chain substituents is perpendicular to that of
the π-system in such bridges.45-51 For comparative purposes, we
have also examined phenyl-based analogues of the fluorenyl-
based o-carboranes, and report comprehensive structural and
spectroscopic characterization of the new compounds, and an
assessment of the impact of the structural modifications on
second-order NLO properties using the hyper-Rayleigh
scattering (HRS) technique.
a. School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122,
Jiangsu Province, China.
E-mail: Mark.Humphrey@anu.edu.au.
b. Current address: Key Laboratory for Advanced Technology in Environmental
Protection of Jiangsu Province, Yancheng Institute of Technology, Yancheng
224051, Jiangsu Province, China
c. Research School of Chemistry, Australian National University, Canberra, ACT
2601, Australia.
d. Current address: China-Australia Joint Research Center for Functional Molecular
Materials, School of Chemical Science and Engineering, Tongji University,
Shanghai 200092, China.
Electronic Supplementary Information (ESI) available: NMR spectra, single-crystal X-
ray diffraction studies details and thermal ellipsoid plots, and overlays of optical
absorption spectra. For ESI and crystallographic data in CIF or other electronic
format, see DOI: 10.1039/x0xx00000x.
This journal is © The Royal Society of Chemistry 20xx
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depicted in Schemes 1-2 and extend the ViewweAlrtli-cklenOonwlinne
displacement of the Lewis bases from decaborane(12)-Lewis
Scheme 1. Preparation of compounds 1, 5 - 8.
DOI: 10.1039/C9DT02645B
base adducts with alkynes52 to a series of new designed alkynes.
The new alkynes 1, 11, 13, 15, and 20 were prepared as depicted
in Schemes 1-2 and as described in the Experimental section;
we note that the synthesis of ethyl53 and hexyl54 analogues of
11 have been reported previously, while the syntheses of 15
and 18 were based on those of their previously-reported hexyl
analogues.55, 56 The new functionalized o-carborane targets
were isolated in fair to good yields and characterized by the
usual spectroscopic and analytical techniques (Experimental
section and ESI Figures S1-S50).
NPh2
NPh2
I
a
1
81%
R
R
B10H12(SEt2)2
R’
R
I
I
R’
b
a
R
Cmpd Yield %
R
R’ Cmpd Yield %
H
Ph
Bu
2
3
4
59
53
46
H
NPh2
5
6
7
8
72
82
94
65
Ph NPh2
Bu NPh2
Bu NO2
The identities of 1, 4-8, 10, 11 and 14 were confirmed by
single-crystal X-ray diffraction studies. Thermal ellipsoid plots
and selected bond lengths for 7 and 8 are given in Figures 1 and
2, respectively, while crystal data for all structures (Tables S1
and S2) and thermal ellipsoid plots and selected bond lengths
for the remaining structures (Figures S51-S57) are collected in
the ESI file. The structural studies shed light on the extent and
The carborane skeletons are drawn as wireframes with the BH vertices as black
balls. a) Pd(PPh3)4, CuI, NEt3, THF (
overnight); b) toluene, reflux 2 days.
1 and 8: reflux, overnight; 5-7: 70 °C,
nature of the p-system in these compounds. They reveal that
Results and discussion
the N-bound phenyl groups are twisted away from co-planarity
with the N-1,4-C6H4 unit in the diphenylamino appended
compounds 1, 5, 6, and 7 and rotated from coplanarity with the
N-2,7-fluorenyl group in the diphenylamino substituted
compounds 10 and 11. As expected, the n-butyl groups are
orthogonal to the fluorenyl plane in 10, 11, and 14. The two
Preparation and characterization of C-functionalized carboranes.
The target compounds consist of o-carboranes with one core C
connected to 1,4-phenyleneethynylene-1,4-phenyl or 2,7-
fluorenyleneethynylene-2,7-fluorenyl backbones functionalized
by electron donating diphenylamino (5-7, 16) or electron
withdrawing nitro groups (8, 17), and the other core C attached
to H (2, 5), Ph (3, 6), n-Bu (4, 7, 8, 16, 17), or a second 7-
diphenylaminofluorenyleneethynylenefluorenyl unit (22). The
syntheses of the target compounds 5-8, 16, 17, and 22 are
phenylene groups in the 1,4-C6H4CºC-1,4-C6H4 units subtend
dihedral angles of 9.84° (1), 40.1(2)° (5), 50.09(8)° (6), 8.5(2)°,
6.3(2)° (7, two crystallographically distinct molecules), and
35.95(9)° (8), the broad range of values emphasizing the soft
Scheme 2. Preparation of compounds 16
,
17 and 22.
HNPh2
SiMe3
K2CO3
Br
Me3Si
b
c
a
NPh2
NPh2
NPh2
Bu
Bu
Bu
Bu
Bu
Bu
Bu
Bu
10
52%
11
85%
NPh2
9
Bu
16
79%
d
Bu
Bu
Bu
C4H9
B10H12(SEt2
)
2
f
I
Bu
Bu
c
Br
Br
e
I
g
I
Bu
Bu
Bu
Bu
Bu
12
90%
Bu
Bu
Bu
Bu
Bu
13
14
57%
NO2 17
50%
Bu
62%
d
Bu Bu
SiMe3
e
K2CO3
TMS
I
NPh2
Bu
NO2
e*
c
Bu
NO2
Bu
Bu
15
85%
Bu
c
K2CO3
Bu
I
Bu
Bu
Bu
Bu
Bu
Bu
NPh2
Bu
Bu
Bu
Bu
11
I
Br
B10H12(SEt2)2
Br
Bu
Bu
I
e
Br
f
d
g
Bu
Bu
Bu
Bu
I
18
86%
19
76%
20
69%
Bu
Bu
Bu
Bu
Bu
21
37%
22
38%
NPh2
Bu
The carborane skeletons are drawn as wireframes with the BH vertices as black balls. a) 1,10-phenanthroline, CuI, K2CO3, DMF; b) Pd2(dba)3, PPh3, CuI, NEt3, THF; c)
MeOH/CH2Cl2; d) Pd(PPh3)4, CuI, NEt3, THF; e) PdCl2(PPh3)2, CuI, NEt3, THF; f) 1. n-BuLi, -78°C; 2. I2, 30 min; g) toluene.
2 | J. Name., 2012, 00, 1-3
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potential energy surface for rotation at the C-C linkages, and the
dominance of crystal packing forces in controlling this structural
View Article Online
DOI: 10.1039/C9DT02645B
Figure 1. Molecular structure of 7, with thermal ellipsoids set at the 40% probability
level. Hydrogen atoms and the second crystallographically distinct molecule have
been omitted for clarity. Selected bond lengths (Å): C1-C2 1.708(8), B(1)-B(3)
1.765(10), B(1)-B(5) 1.754(10), B(1)-B(7) 1.746(10), B(1)-C(1) 1.716(10), B(1)-C(2)
1.712(9), B(2)-B(4) 1.777(9), B(2)-B(6) 1.790(9), B(2)-B(8) 1.774(9), B(2)-C(1) 1.725(9),
B(2)-C(2) 1.728(8), B(3)-B(4) 1.770(11), B(3)-B(7) 1.768(11), B(3)-B(9) 1.779(10), B(3)-
C(1) 1.704(9), B(4)-B(8) 1.779(10), B(4)-B(9) 1.775(10), B(4)-C(1) 1.705(8), B(5)-B(6)
1.779(10), B(5)-B(7) 1.778(10), B(5)-B(10) 1.787(10), B(5)-C(2) 1.703(9), B(6)-B(8)
1.775(9), B(6)-B(10) 1.786(9), B(6)-C(2) 1.711(8), B(7)-B(9) 1.790(10), B(7)-B(10)
1.801(10), B(8)-B(9) 1.787(10), B(8)-B(10) 1.792(11), B(9)-B(10) 1.791(10).
Figure 2. Molecular structure of 8, with thermal ellipsoids set at the 40% probability
level. Hydrogen atoms have been omitted for clarity. Selected bond lengths (Å): C1-
C2 1.702(3), B(1)-B(3) 1.769(4), B(1)-B(5) 1.767(4), B(1)-B(7) 1.762(4), B(1)-C(1)
1.724(3), B(1)-C(2) 1.734(3), B(2)-B(4) 1.769(4), B(2)-B(6) 1.792(4), B(2)-B(8) 1.774(4),
B(2)-C(1) 1.731(4), B(2)-C(2) 1.730(3), B(3)-B(4) 1.781(4), B(3)-B(7) 1.768(4), B(3)-B(9)
1.778(4), B(3)-C(1) 1.711(4), B(4)-B(8) 1.787(4), B(4)-B(9) 1.778(4), B(4)-C(1) 1.709(3),
B(5)-B(6) 1.777(4), B(5)-B(7) 1.769(4), B(5)-B(10) 1.776(4), B(5)-C(2) 1.705(3), B(6)-
B(8) 1.781(4), B(6)-B(10) 1.783(4), B(6)-C(2) 1.709(3), B(7)-B(9) 1.785(4), B(7)-B(10)
1.785(4), B(8)-B(9) 1.779(4), B(8)-B(10) 1.793(4), B(9)-B(10) 1.785(4).
parameter. These data also reinforce the benefit of progressing from width: ca. 20 ns, maximum pulse strength: 200 mJ) and the
phenyl-based bridges to 16, 17, and 22, with fluorenyl bridging units internal reference method was used to derive the < HRS values.
We note that the compounds are optically transparent at the
b
>
and enforced bridge planarity.
fundamental and second-harmonic wavelengths. In the case of
samples for which the signal observed was essentially HRS-only,
and little to no scattering was seen at wavelengths around 532
Linear optical and quadratic NLO studies
UV-vis-NIR data were obtained for 1, 5-8, 16, 17, and 22 in
CH2Cl2 solutions, the key parameters being collected in Table 1.
Replacing the terminal phenyl unit in 1 with an o-carborane
unit, in proceeding to 5-7, results in a small red shift in optical
absorption maximum, consistent with the carborane unit
functioning as a weak-to-moderate strength acceptor group in
the ground state. Proceeding from the D-B-A composition of 7
to an A-B-A composition in 8 leads to a blue shift in lmax, as
anticipated. Replacing the bridge 1,4-phenylene units in 7 and 8
with 2,7-fluorenylene units to afford 16 and 17, respectively,
nm (viz. 5-8, 16, 17), the uncertainty in the measured <b>
HRS
data was estimated to be ca. 10%, similar to that reported for
most published HRS data. In contrast, 1 and 22 displayed strong
non-HRS scattering at wavelengths near 532 nm (evidenced by
strong scattering signals at 533 nm and 531 nm), and in these
cases the estimated uncertainty in the measured <b>HRS was ca.
25% (this increased error margin resulted from the (reasonable)
assumption that the broad non-HRS scattering has the same
strength at 532 nm as at 533 nm and 531 nm). No measurable
HRS signals were observed for the 4-iodophenyl or 2-
iodofluorenyl-functionalized carboranes 3, 4, and 14,
demonstrating the necessity of incorporating a polarizing
leads to a significant red-shift in location of lmax for the former
and a dramatic red-shift in the location of this band for the
latter, consistent with bridge extension and planarization.
However, introduction of
fluorenyl-containing unit, proceeding from 16 to 22, leads to no
change in max and a doubling in the value, both observations
a second NPh2-functionalized
diphenylamino or nitro substituent. The <
b
>
values in Table
0> values were
HRS
1 are the measured <
calculated from:58
b
> values, and the <
b
l
e
being consistent with no extension of the effective
and independent fluorenyl-containing bridges.
p-system
<
b
>
HRS = <
b
0> D0(
l
) and D0(
l
) = 1/ [ (1-l2
/l
2) (1-4 l2
/ ]
l2)
max
max
The quadratic NLO properties were assessed by the hyper-
Rayleigh scattering procedure, using an experimental set-up
and data analysis that we have described in detail elsewhere.57
A Nd-YAG laser was used to generate the fundamental light
employed in the current studies (wavelength: 1064 nm, pulse
where
optical absorption maxima
corresponding UV-Vis spectra.
l is the fundamental wavelength (1064 nm) and the
l
max values were obtained from the
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The lmax values are 148-203 nm removed from the second- this NLO-efficient compound (and related examples somewhat
View Article Online
DOI: 10.1039/C9DT02645B
harmonic wavelength of 532 nm and span a comparatively less efficient) are significantly less optically transparent (lmax
narrow range of 55 nm. As a result, the <
twice the size of the < 0> values and the broad trend in data is harmonic wavelength (532 nm). o-Carborane functionalized
maintained on proceeding from < to < 0> values. Several with a 1,4-phenylethynylfullerene[60] exhibited a resonance-
observations can be made. First, replacing the terminal phenyl enhanced
value of 346 x 10-30 esu (ns pulses, HRS, 1064 nm),
b
>
values are ca. 463 nm) and may exhibit residual absorbance at the second-
HRS
b
b
>
b
HRS
b
group in 1 by an electron-withdrawing o-carborane unit but the authors noted residual absorptivity of up to 1000 M-1
(proceeding to 5) results in a significant increase in quadratic cm-1 at 532 nm,20 in contrast to the compounds in the present
nonlinearity. Second, introduction of weakly electron-donating study which are transparent at the measurement wavelength
phenyl or n-butyl groups (proceeding from 5 to 6 or 7) results in (Figure S58). The transparency exhibited by the present series
a small decrease in nonlinearity, of the order of the error of compounds, coupled to the stability inherent in the
margins of these measurements. Third, replacement of the carborane unit, the possibility of incorporating solubilizing
electron-donating diphenylamino group by an electron- substituents out of the plane of the p-system (n-butyl groups in
withdrawing nitro group (proceeding from 7 to 8, and thereby the present work), and the increase in NLO performance to be
from a D-B-A assembly to an A-B-A construction) leads to a anticipated on progressing from o-Cb to m- and p-functionalized
significant decrease in nonlinearity, as anticipated. Fourth, carboranes, suggest that considerable opportunity exists in
replacement of the 1,4-phenylene bridge unit by 9,9-di-n-butyl- exploiting C-functionalized carboranes in NLO applications.
2,7-fluorenylene groups (proceeding from 7 to 16 or 8 to 17) Further studies addressing this potential are currently
results in a doubling or greater of the quadratic NLO coefficient. underway.
Fifth, introduction of a second 9,9-di-n-butyl-2,7-fluorenylene
group in place of an n-butyl group at the o-carborane core
Experimental
(proceeding from 16 to 22) results in a further 30-40% increase
in the coefficients.
b
General Procedures. All reactions were carried out under
Schlenk conditions unless otherwise stated. Commercially
available materials were used as received. Tetrahydrofuran and
toluene were dried by distilling over sodium/benzophenone,
and dichloromethane was dried by distilling over calcium
hydride. Petrol refers to a fraction of petroleum spirits with a
While the present study was targeted at establishing the
structure-NLO property outcomes in the preceding paragraph,
we note that the absolute quadratic NLO values for the present
compounds are large compared to extant data for o-Cb dyads.
For example, o-carborane C-functionalized by (1,4-phenylene-
E-vinylene)ferrocenyl groups exhibits a
and a
b
value of 114 x 10-30 esu
boiling range 60-80 °C. Chromatography was on silica gel
b
0 value of 66 x 10-30 esu (ns pulses, HRS, 1064 nm),21 but
(Aldrich, 200-300 mesh) or basic alumina (100-200 mesh).
B10H12(SEt2)2,59 4-ethynyl-N,N-diphenylaniline,60 4-ethynyl-1-
iodobenzene and 4-ethynyl-1-nitrobenzene,61 4-(hex-1-yn-1-
yl)-1-iodobenzene,62 1-iodo-4-phenylethynylbenzene,63 7-
bromo-9,9-di-n-butyl-2-iodo-9H-fluorene,56 9,9-di-n-butyl-7-
ethynyl-2-nitro-9H-fluorene,64 and 1-(4-iodophenyl)-1,2-
ortho-carborane (2)8 were prepared following literature
procedures.
Table 1. Linear optical and quadratic NLO parameters.
NPh2
NPh2
NPh2
1
Bu
Bu
R
R = H
R = Ph
R = Bu
5
6
7
Bu
Bu
Instrumentation. Mass spectra were recorded at the
Bu
Australian
National
University
(ANU)
using
a
Micromass/Waters LCT-ZMD single quadrupole liquid
chromatograph-MS (ESI MS, both unit resolution and HR), a VG
Quattro II triple quadrupole MS (EI MS, unit resolution) and a
VG AutoSpec M series sector (EBE), or at Jiangnan University
using a Micromass/Waters Quattro Micro API (ESI-MS) or a
Bruker SCIONSQ-456-GC gas chromatograph (EI-MS).
Microanalyses were carried out at the School of Human
Sciences, Science Centre, London Metropolitan University, U.K.
1H NMR spectra were recorded using Varian Mercury-300,
Varian Gemini-300 or Bruker AVANCE III-400 FT-NMR
spectrometers, and are referenced to residual chloroform
(7.26 ppm). 13C NMR spectra were recorded using Varian
Inova-500 or Bruker AVANCE III-400 FT-NMR spectrometers
and are referenced to d-chloroform (77.0 ppm). 11B NMR
spectra were recorded using Varian Mercury-300, Varian
Gemini-300 or Bruker AVANCE III-400 FT-NMR spectrometers,
and are referenced to external BF3.Et2O (0.0 ppm). UV-vis-NIR
spectra were recorded as CH2Cl2 solutions in 1 cm quartz cells
8
NO2
Bu
Bu
Bu
Bu
R’
Bu
Bu
NPh2
Bu
22
R’ = NPh2 16
R’ = NO2 17
Bu
Bu
b
Sample
1
5
6
7
l
max [e]a
<b>HRS
85 ± 20
<b0>b
41
61
56
48
24
96
61
129
361 [1.7]
367 [3.5]
371 [3.8]
370 [3.8]
329 [3.0]
384 [6.4]
377 [4.5]
384 [12.6]
131 ± 13
123 ± 12
105 ± 10
43 ± 4
230 ± 23
141 ± 14
309 ± 77
8
16
17
22
The carborane skeletons are drawn as wireframes with the BH vertices as black balls.
a) CH2Cl2 solutions. lmax in nm [e in 104 M-1 cm-1]. b) THF solutions. <b> and <b0> in 10-
30 esu (1064 nm, 20 ns). Errors in <b0> propagated from those of the <b>HRS values.
4 | J. Name., 2012, 00, 1-3
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using Cary 5 or Lambda TU1901 spectrophotometers, and are N,N-diphenylaniline (180 mg, 0.67 mmol) were added to
View Article Online
lmax nm (e
104 M-1 cm-1). IR spectra were recorded deoxygenated NEt3/THF (1:1, 40 mL). Pd(PPh3)4 (35 mg, 0.030
DOI: 10.1039/C9DT02645B
reported as
using a Thermo Fisher Nicolet 6700 ATR FT-IR spectrometer.
mmol) and CuI (12 mg, 0.063 mmol) were then added and the
Synthesis of Ph-1,4-C6H4C≡C-1,4-C6H4NPh2 (1). A stirred solution stirred at 70°C overnight. After the removal of solvent,
solution of 4-ethynyl-N,N-diphenylaniline (155 mg, 0.58 mmol) the residue was purified through silica gel column
and 4-iodobiphenyl (200 mg, 0.71 mmol) in NEt3/THF (1:1, 30 chromatography, eluting with hexane/CH2Cl2 (v/v = 8/1).
mL ) was deoxygenated via three freeze-pump-thaw cycles and Recrystallization from hexane afforded the target compound as
then purged with N2. Pd(PPh3)4 (17 mg, 0.015 mmol) and CuI (8 an off-white solid (213 mg, 0.44 mmol, 72%). 1H NMR (400 MHz,
mg, 0.042 mmol) were then added and the solution heated at CDCl3): δ 7.44 (s, 4H), 7.37 (d, J = 8 Hz, 2H), 7.29 (t, J = 8 Hz, 4H),
reflux overnight. The solvent was removed under vacuum, and 7.17-7.05 (m, 6H), 7.01 (d, J = 9 Hz, 2H), 3.95 (s, 1H), 3.47-1.65
the residue purified by silica thin-layer chromatography eluting (br, 10H, BH). 13C NMR (101 MHz, CDCl3): δ 148.4, 147.1, 132.7,
with petrol. Removal of solvent and recrystallization from petrol 132.6, 131.6, 129.5, 127.6, 125.8, 125.2, 123.8, 122.0, 115.1,
afforded compound 1 as a white solid (200 mg, 0.47 mmol, 92.5, 87.1, 76.2, 60.2. 11B NMR (128 MHz, CDCl3): δ -1.37, -2.55,
81%). Rf - 0.4 (petrol). 1H NMR (400 MHz, CDCl3): δ 7.72-7.59 (m, -8.27, -9.48, -10.13, -11.43. FT-IR (KBr, cm-1): 2603 (br, B-H),
6H), 7.56-7.38 (m, 5H), 7.28-7.33 (t, J = 8 Hz, 4H), 7.25-7.01 (m, 2201 (w, Cº
C), 1279 (s, C-N). MS (EI) m/z (%): 487.3 ([M+], 100).
8H). 13C NMR (101 MHz, CDCl3): δ 147.9, 147.2, 140.6, 140.4, HRMS (EI): Calc. for C28H28B10N ([M – H]+): 488.3152, found
132.5, 131.9, 129.4, 128.8, 127.5, 127.0, 125.0, 123.5, 122.5, 488.3159. Anal. Calcd for C28H29B10N: C, 68.96; H, 5.99; N,
122.3, 116.1, 90.4, 88.6. FT-IR (KBr, cm-1): 2214 (w, C
(s, C-N). MS (EI): m/z (%): 421.2 (100, [M]+). HRMS (EI): Calc. for
C32H23N: 421.1830, found 421.1831. Anal. Calcd for C32H23N: C, ortho-carborane (6). Compound 3 (845 mg, 2.00 mmol) and 4-
91.18; H, 5.50; N, 3.32. Found: C, 90.96; H, 5.58; N, 3.44. ethynyl-N,N-diphenylaniline (539 mg, 2.00 mmol) were added
º
C), 1270 2.87 %. Found: C, 68.84; H, 6.00; N, 2.85%.
Synthesis of 2-phenyl-1-(Ph2N-1-C6H4-4-C≡C-4-C6H4-1)-1,2-
Synthesis of 2-phenyl-1-(4-iodophenyl)-1,2-ortho-carborane to deoxygenated NEt3/THF (1:1, 40 mL). Pd(PPh3)4 (46 mg, 0.040
(3). To a solution of B10H12(SEt2)2 (3.58 g, 11.9 mmol) in dry mmol) and CuI (15 mg, 0.078 mmol) were added and the
toluene (50 mL) was added 1-phenylethynyl-4-iodobenzene solution stirred at 70°C overnight. The solvent was removed
(3.04 g, 13.3 mmol). The reaction mixture was heated at reflux under vacuum, and the residue purified by silica plate thin-layer
for 2 days, after which MeOH was added to quench the chromatography, eluting with petrol /CH2Cl2 (2:1). The solvent
reaction. The solvent was removed in vacuum, and the residue was removed. Crystallization from petrol/CH2Cl2 afforded
was purified by silica column chromatography, eluting with compound 6 as needle-like crystals. (921 mg, 1.63 mmol, 82%).
petrol. The solvent was reduced in volume to give compound 3 1H NMR (400 MHz, CDCl3): δ 7.45 (d, J = 8 Hz, 2H), 7.39 (d, J = 9
1
as a white solid (2.95 g, 6.99 mmol, 53%). Rf -0.7 (hexane). H Hz, 2H), 7.33-7.25 (m, 9H), 7.18-7.07 (m, 8H), 6.99 (d, J = 9 Hz,
NMR (400 MHz, CDCl3): δ 7.51 - 7.45 (m, 4H), 7.30 (t, J = 7 Hz, 2H), 3.65-1.68 (br, 10H, BH). 13C NMR (101 MHz, CDCl3): δ 148.4,
1H), 7.18 (dd, J = 17, 8 Hz, 4H), 3.83 - 1.62 (br, 10H, BH). 13C NMR 147.0, 132.6, 131.1, 130.62, 130.55, 130.5, 130.3, 123.0, 129.5,
(101 MHz, CDCl3): δ 137.5, 132.1, 130.6, 130.6, 130.4, 130.4, 128.4, 125.8, 125.2, 123.8, 121.9, 115.1, 92.6, 87.3, 85.5, 84.8.
128.5, 97.2, 85.3, 84.2. 11B NMR (128 MHz, CDCl3): δ -1.70, - 11B NMR (128 MHz, CDCl3): δ -1.78, -2.87, -9.73, -10.82. FT-IR
2.84, -8.47, -9.68, -10.83, -12.11. FT-IR (KBr, cm-1): 2580 (s, B‒ (KBr, cm-1): 2591 (s, B-H), 2217 (m, C
ºC), 1275 (s, C-N). MS (EI)
H). HRMS (EI): Calc. Mass for C14H18B10I ([M – H]+): 423.1384, m/z (%): 564.3 ([M - H]+, 100). HRMS (EI): Calcd for C34H33B10N
found 423.1381. Anal. Calcd for C14H19B10I: C, 39.82; H, 4.53. 563.3632, found 563.3643. Anal. Calcd for C34H33B10N: C, 72.44;
Found: C, 39.92; H, 4.69.
H, 5.90; N, 2.48 %. Found: C, 72.43; H, 6.03; N, 2.54 %.
Synthesis of 2-n-butyl-1-(4-iodophenyl)-1,2-ortho-carborane
Synthesis of 2-(n-butyl)-1-(Ph2N-1-C6H4-4-C≡C-4-C6H4-1)-1,2-
(4). B10H12(SEt2)2 (2.33 g, 7.75 mmol) and 4-(hex-1-yn-1-yl)-1- ortho-carborane (7). Compound 4 (500 mg, 1.24 mmol) and 4-
iodobenzene (2.00 g, 7.04 mmol) were added to dry toluene (40 ethynyl-N,N-diphenylaniline (368 mg, 1.37 mmol) were added
mL). The reaction mixture was heated at reflux for 2 days, after to deoxygenated NEt3/THF (1:1, 40 mL). Pd(PPh3)4 (80 mg, 0.069
which MeOH was added to quench the reaction. The solvent mmol) and CuI (30 mg, 0.16 mmol) were then added and the
was then removed and the residue was purified by basic solution stirred at 70 °C overnight. The solvent was removed
alumina column chromatography, eluting with hexane. The under vacuum, and the residue was purified by silica thin-layer
solvent was reduced in volume to give compound 4 as a white chromatography, eluting with petrol. The solvent was removed
1
solid (1.30 g, 3.23 mmol, 46%). Rf - 0.8 (hexane). H NMR (400 to give a white solid. Recrystallization from methanol afforded
MHz, CDCl3) δ 7.75 (d, J = 9 Hz, 2H), 7.37 (d, J = 9 Hz, 2H), 3.29- compound 7 as a flaky white solid (630 mg, 1.16 mmol, 94%). Rf
1.55 (br, 10H, BH), 1.82-1.70 (m, 2H), 1.77 (m, 2H), 1.39 (m, 2H), - 0.4 (petrol). 1H NMR (400 MHz, CDCl3): δ 7.58 (d, J = 9 Hz, 2H),
1.14 (dq, J = 15, 7 Hz, 2H), 0.79 (t, J = 7 Hz, 3H). 13C NMR (101 7.48 (d, J = 9 Hz, 2H), 7.36 (d, J = 9 Hz, 2H), 7.30 - 7.26 (dd, J = 9,
MHz, CDCl3): δ 138.1, 132.7, 130.7, 97.5, 82.6, 82.5, 34.9, 31.5, 7 Hz, 4H), 7.13-7.06 (m, 6H), 7.00 (d, J = 9 Hz, 2H), 2.51 (br, 10H,
22.1, 13.5. 11B NMR (128 MHz, CDCl3): δ -2.98, -4.18, -9.68, - BH), 1.76 (m, 2H), 1.36 (dt, J = 16, 6 Hz, 2H), 1.10 (m, 2H), 0.76
10.68. FT-IR (KBr, cm-1): 2627-2555 cm-1 (s, B-H). HRMS (EI): (t, J = 7 Hz, 3H). 13C NMR (101 MHz, CDCl3): δ 148.5, 147.0, 132.7,
Calc. for C12H21B10I ([M – 2H]+): 402.1619, found 402.1615. Anal. 131.6, 131.1, 130.0, 129.5, 125.2, 123.8, 121.9, 115.0, 92.8,
Calcd for C12H23B10I: C, 35.82; H, 5.76. Found: C, 35.87; H, 5.64. 87.2, 83.2, 82.8, 34.8, 31.5, 22.1, 13.5. 11B NMR (128 MHz,
Synthesis of 1-(Ph2N-1-C6H4-4-C≡C-4-C6H4-1)-1,2-ortho- CDCl3): δ -3.14, -4.16, -9.72, -10.67. FT-IR (KBr, cm-1): 2583 (br,
carborane (5). Compound 2 (211 mg, 0.61 mmol) and 4-ethynyl- B-H), 2211 (m, C
º
C). MS (EI): m/z (%): 543.4 (100, [M]+). HRMS
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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Page 6 of 11
ARTICLE
(EI): Calc. for C32H35B10N ([M – 2H]+): 543.3700, found 543.3703.
Journal Name
Synthesis
of
9,9-di(n-butyl)-2-(N,N-dipheVnieywlaAmrticilne oO)n-li7ne-
DOI: 10.1039/C9DT02645B
Anal. Calcd for C32H37B10N: C, 70.68; H, 6.86; N, 2.58. Found C, (ethynyl)-9H-fluorene (11). Compound 10 (0.45 g, 0.83 mmol)
70.79; H, 6.93; N, 2.47.
was added to a mixture of deoxygenated CH2Cl2/methanol (1:1,
Synthesis of 2-(n-butyl)-1-(O2N-1-C6H4-4-C≡C-4-C6H4-1)-1,2- 20 mL). K2CO3 (0.230 g, 1.66 mmol) was added and the mixture
ortho-carborane (8). Compound 4 (300 mg, 0.75 mmol) and 4- stirred for 4 h. The solvent was removed under reduced
ethynyl-1-nitrobenzene (121 mg, 0.82 mmol) were added to pressure and flash-filtered through alumina (eluent: CCl4) to
deoxygenated NEt3/THF (1:1, 40 mL). Pd(PPh3)4 (50 mg, 0.043 give compound 11 as a pale yellow solid (332 mg, 0.71 mmol,
mmol) and CuI (8.0 mg, 0.042 mmol) were then added and the 85%). Rf - 0.2 (hexane). 1H NMR (400 MHz, CDCl3) : δ 7.59-7.56
solution heated at reflux overnight. The solvent was removed (dd, J = 8, 3 Hz, 2H), 7.50-7.46 (m, 2H), 7.31-7.27 (m, 4H), 7.17-
under vacuum, and the residue purified by silica thin-layer 7.13 (m, 5H), 7.07-7.04 (m, 3H), 3.15 (s, 1H), 1.91-1.85 (m, 4H),
chromatography, eluting with a petrol/CH2Cl2 (2:1) mixture. 1.12-1.10 (m, 4H), 0.76-0.24 (t, J = 7 Hz, 6H), 0.70-0.60 (m, 4H).
Recrystallization afforded a flaky white solid (205 mg, 0.49 13C NMR (101 MHz, CDCl3): δ 152.5, 150.6, 147.9, 147.8, 141.8,
1
mmol, 65%). Rf - 0.5 (petrol/CH2Cl2 = 2:1). H NMR (400 MHz, 135.2, 131.2, 129.2, 126.4, 124.0, 123.3, 122.7, 120.8, 119.3,
CDCl3): δ 8.26 (d, J = 9 Hz, 2H), 7.72 - 7.67 (dd, J = 11, 9 Hz, 4H), 118.94, 118.92, 84.9, 55.0, 39.9, 26.0, 23.0, 13.9. FT-IR (KBr, cm-
7.59 (d, J = 8 Hz, 2H), 3.35 - 1.80 (br, 10H, BH), 1.82-1.77 (m, 2H), 1): 2101 (w, C
ºC), 3299 (m, ºCH). HRMS (EI): Calc. for C35H35N:
1.44 - 1.36 (dt, J = 16, 8 Hz, 2H), 1.13 (dd, J = 15, 7 Hz, 2H), 0.78 469.2770, found 469.2778. Anal. Calcd for C35H35N: C, 89.51; H,
(t, J = 7 Hz, 3H). 13C NMR (101 MHz, CDCl3): δ 147.4, 132.5, 132.1, 7.51; N, 2.98. Found: C, 89.51; H, 7.63; N, 2.87.
131.5, 131.3, 129.4, 124.7, 123.7, 92.7, 90.0, 82.8, 82.7, 34.9,
31.5, 22.1, 13.5. 11B NMR (128 MHz, CDCl3): δ -3.15, -4.22, -9.50, fluorene (12). 7-Bromo-9,9-di(n-butyl)-2-iodo-9H-fluorene
-10.69. FT-IR (KBr, cm-1): 2613-2579 (s, B-H); 2217 cm-1 (w, C
C); (6.00 g, 12.42 mmol) in NEt3/THF (20/20 mL) was deoxygenated
Synthesis of 2-bromo-9,9-di(n-butyl)-7-(hex-1-yn-1-yl)-9H-
º
1518, 1340 (NO2). MS (EI): m/z (%): 421 (100, [M]+). HRMS (EI): via two freeze-pump-thaw cycles and then purged with N2. To
Calc. for C20H27B10NO2: 421.3056, found 421.3054. Anal. Calcd this solution was added PdCl2(PPh3)2 (0.175 g, 0.25 mmol), CuI
for C20H27B10NO2: C, 56.98; H, 6.46; N, 3.32. Found: C, 56.87; H, (0.095 g, 0.50 mmol), and 1-hexyne (1.60 mL, 14.0 mmol), and
6.36; N, 3.51.
the mixture was stirred at RT for 10 h. The solvent was then
Synthesis
of
9,9-di(n-butyl)-2-(N,N-diphenylamino)-7- removed under reduced pressure and the residue was purified
((trimethylsilyl)ethynyl)-9H-fluorene (10). A mixture of 2- by silica column chromatography using hexane as eluent.
bromo-9,9-di(n-butyl)-7-iodo-9H-fluorene (9.66 g, 20.0 mmol), Compound 12 was obtained as a pale-yellow oil following
1
diphenylamine (2.20 g, 13.0 mmol), copper(I) iodide (248 mg, removal of the solvent (4.91 g, 90 %). Rf - 0.7 (petrol). H NMR
1.30 mmol), 1,10-phenanthroline (468 mg, 2.60 mmol) and (400 MHz, CDCl3): δ 7.57 (d, J = 8 Hz, 1H), 7.51 (d, J = 9 Hz, 1H),
potassium carbonate (4.00 g, 24.6 mmol) was purged with 7.47-7.41 (m, 2H), 7.41-7.32 (m, 2H), 2.45 (t, J = 7 Hz, 2H), 1.97-
nitrogen, and then 30 mL of anhydrous DMF was added. The 1.86 (m, 4H), 1.69-1.58 (m, 2H), 1.56-1.46 (m, 2H), 1.07 (dd, J =
mixture was heated to reflux for 24 h. After cooling to room 15, 7 Hz, 4H), 0.97 (t, J = 7 Hz, 3H), 0.67 (t, J = 7 Hz, 6H), 0.60-
temperature, the dark suspension was poured into ice-water. 0.48 (m, 4H). 13C NMR (101 MHz, CDCl3): δ 153.1, 150.3, 139.6,
The precipitate was collected and purified by silica gel column 139.5, 130.7, 130.0, 126.1, 125.9, 122.9, 121.2, 121.2, 119.6,
chromatography, eluting with petrol to obtain 2-bromo-9,9- 90.7, 81.3, 55.3, 40.1, 30.9, 25.8, 23.0, 22.1, 19.3, 13.8, 13.7. FT-
di(n-butyl)-N,N-diphenylamino-9H-fluorene (9) as a white solid IR (KBr, cm-1): 2227 cm-1 (C
(3.06 g, 45%). Rf - 0.50 (petrol). A stirred solution of 9 (1.05 g, 436.1766, found 436.1764.
ºC).
HRMS (EI): Calc. for C27H3379Br:
2.01 mmol) in NEt3 (10 mL) and THF (20 mL) was then
Synthesis of 9,9-di(n-butyl)-7-(hex-1-yn-1-yl)-2-iodo-9H-
deoxygenated via three freeze-pump-thaw cycles and then fluorene (13). Compound 12 (2.10 g, 4.80 mmol) was added to
purged with argon. To this mixture was added PPh3 (21 mg, THF (30 mL) and cooled to -78 °C. n-BuLi (3.6 mL of a 1.6 M
0.080 mmol), Pd2(dba)3 (37 mg, 0.040 mmol) and CuI (8 mg, solution in hexane, 5.76 mmol) was slowly added via syringe and
0.042 mmol), followed by trimethylsilylacetylene (0.295 g, 3.00 the mixture stirred for 2 h. Iodine (1.82 g, 7.17 mmol) in THF (25
mmol, 0.42 mL). This mixture was then sealed and stirred at mL) was added and the mixture warmed to RT. After 30 min
85 °C overnight. After cooling to room temperature, the mixture stirring, aqueous Na2S2O3 was added and the mixture extracted
was reduced in volume, and flash-filtered through alumina with CH2Cl2, washing well with water. The CH2Cl2 layer was dried
(eluent: CCl4). The solvent was removed in vacuo to afford a with MgSO4 and the solvent removed. The residue was purified
brown solid. Purification via TLC on silica gel (eluent: by silica column chromatography, eluting with petrol. The
cyclohexane) gave compound 10 as a pale yellow solid (0.55 g, solvent was removed to give compound 13 as a pale-yellow oil
1
1
1.01 mmol, 51 %). Rf -0.3 (cyclohexane). H NMR (400 MHz, (1.44 g, 2.97 mmol, 43 %). Rf - 0.6 (petrol). H NMR (400 MHz,
CDCl3): δ 7.53-7.51 (m, 2H), 7.44-7.38 (m, 2H), 7.24 (t, J = 8 Hz, CDCl3): δ 7.84-7.15 (m, 6H), 2.53-2.46 (m, 2H), 2.04-1.92 (m,
4H), 7.12-7.09 (m, 5H), 7.03-6.99 (m, 3H), 1.84 (dd, J = 16, 8 Hz, 4H), 1.72-1.62 (m, 2H), 1.60-1.52 (m, 2H), 1.12 (dd, J = 15, 7 Hz,
4H), 1.13-1.00 (m, 4H), 0.69 (dd, J = 8, 7 Hz, 6H), 0.63 (m, 4H), 4H), 1.05-0.97 (m, 3H), 0.71 (dd, J = 9, 6 Hz, 6H), 0.61 (dt, J = 10,
0.28 (s, 9H). 13C NMR (101 MHz, CDCl3): δ 152.5, 150.49, 147.9, 7 Hz, 4H). 13C NMR (101 MHz, CDCl3): δ 153.3, 150.1, 140.3,
147.7, 141.3, 135.5, 131.3, 129.2, 126.1, 124.0, 123.3, 122.7, 139.6, 136.0, 132.1, 130.7, 130.6, 125.8, 123.1, 121.6, 119.6,
120.71, 119.0, 118.9, 106.5, 93.6, 55.0, 40.0, 26.0, 23.0, 13.9, 92.9, 90.8, 81.4, 55.3, 40.2, 25.9, 23.1, 22.2, 19.3, 13.8, 13.7. FT-
0.1. FT-IR (KBr, cm-1): 2154 (m, C
C38H43NSi: 541.3165, found 541.3168.
º
C
.
HRMS (EI): Calc. for IR (KBr, cm-1): 2226 cm-1 (C
484.1627, found 484.1628.
ºC). HRMS (EI): Calc. for C27H33I:
6 | J. Name., 2012, 00, 1-3
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Page 7 of 11
Dalton Transactions
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Journal Name
ARTICLE
2-(n-butyl)-1-(9,9-di(n-butyl)-2-iodo-9H- 1.20 – 1.01 (m, 10H), 0.81 – 0.42 (m, 23H). 13C NMR (101 MHz,
Synthesis
of
View Article Online
fluoren-7-yl)-1,2-ortho-carborane (14).
A
solution of CDCl3): δ 152.5, 151.5, 151.4, 150.7, 147.D9O, 1I:4107..170,319/4C29.D9T, 0124614.55B,
compound 13 (0.710 g, 1.47 mmol) and B10H12(SEt2)2 (0.530 g, 139.4, 135.4, 130.9, 130.8, 130.5, 129.6, 129.2, 126.0, 125.8,
1.76 mmol) in dry toluene (50 mL) was heated at reflux for 3 125.6, 124.0, 123.3, 123.1, 122.7, 120.7, 120.44, 120.36, 120.0,
days and then cooled to room temperature. MeOH was added 119.2, 118.9, 91.5, 89.9, 84.4, 82.8, 55.4, 55.1, 40.0, 39.9, 34.8,
to quench the reaction. The solvent was removed under 31.5, 26.0, 23.0, 22.9, 22.2, 13.9, 13.8, 13.4. 11B NMR (128 MHz,
vacuum. The residue was purified by silica column CDCl3): δ -3.96, -10.51. FT-IR (KBr, cm-1): 2585 (br, B-H), 2201 (w,
chromatography, eluting with petrol. The solvent was reduced
CºC). Anal. Calcd for C62H77B10N: C, 78.85; H, 8.22; N, 1.48.
in volume to give compound 14 as a white solid (0.505 g, 0.84 Found: C, 78.94; H, 8.36; N, 1.57. HRMS (TOF-MS-ES): Calc. for
mmol, 57%). Rf - 0.5 (petrol). 1H NMR (400 MHz, CDCl3): δ 7.73- C62H76B10N ([M – H]+): 944.6908, found 944.6898. Anal. Calcd for
7.38 (m, 6H), 3.7-1.7 (m, 16H, BH), 2.03-1.79 (m, 6H), 1.42-1.34 C62H77B10N: C, 78.85; H, 8.22; N, 1.48. Found: C, 78.94; H, 8.36;
(m, 2H), 1.11-1.04 (m, 6H), 0.75-0.67 (m, 9H), 0.64-0.49 (m, 4H). N, 1.57 %.
13C NMR (101 MHz, CDCl3): δ 153.6, 150.6, 142.5, 139.1, 136.3,
Synthesis of 2-(n-butyl)-1-(2-((9,9-di(n-butyl)-2-nitro-9H-
132.3, 130.6, 129.9, 125.5, 122.1, 119.9, 94.1, 84.3, 82.7, 55.5, fluoren-7-yl)ethynyl)-9,9-di(n-butyl)-9H-fluoren-7-yl)-1,2-
39.7, 34.8, 31.5, 26.0, 22.9, 22.2, 13.7, 13.4. 11B NMR: (128 MHz, ortho-carborane (17). Compounds 14 (240 mg, 0.40 mmol) and
CDCl3) δ -3.20, -4.17, -9.92, -10.79. FT-IR (KBr, cm-1): 2596-2584 15 (138 mg, 0.40 mmol) were dissolved in deoxygenated
(s, B-H). MS (EI): m/z (%): 602.3 (100, [M]+). HRMS (EI): Calc. for NEt3/THF (1:1, 40 mL). Pd(PPh3)4 (15 mg, 0.013 mmol) and CuI
C27H41B10I ([M – 2H]+): 602.3184, found 602.3192. Anal. Calcd (5.0 mg, 0.026 mmol) were then added and the solution heated
for C27H43B10I (%): C, 54.73, H, 5.61. Found: C, 54.86, H, 5.80.
at reflux overnight. The solvent was removed under vacuum,
Synthesis of 9,9-di(n-butyl)-7-ethynyl-2-nitro-9H-fluorene and the residue purified by silica thin-layer chromatography,
(15). A stirred solution of 9,9-di(n-butyl)-2-iodo-7-nitro-9H- eluting with petrol/CH2Cl2 (3:1). The solvent was reduced in
fluorene (4.00 g, 8.90 mmol) in NEt3 and THF (1:1, 40 mL) was volume to give compound 17 as a yellow solid (166 mg, 0.20
1
deoxygenated via three freeze-pump-thaw cycles, and then mmol, 50%). Rf - 0.5 (petrol/CH2Cl2 = 3:1). H NMR (400 MHz,
purged with argon. To this mixture was added PdCl2(PPh3)2 (180 CDCl3): δ 8.28 (dd, J = 8.3, 2.1 Hz, 1H), 8.22 (d, J = 1.6 Hz, 1H),
mg, 0.26 mmol) and CuI (80 mg, 0.42 mmol), and then 7.81 (d, J = 5.6 Hz, 1H), 7.79 (d, J = 5.0 Hz, 1H), 7.73 (d, J = 7.8
trimethylsilylacetylene (1.31 g, 13.3 mmol, 1.9 mL) was added Hz, 1H), 7.69 (d, J = 8.1 Hz, 1H), 7.67 – 7.52 (m, 6H), 3.26 – 2.19
via syringe. The mixture was stirred at 60 °C overnight. After (br, m, 10H, BH), 2.20 – 1.95 (m, 8H), 1.93 – 1.68 (m, 2H), 1.36
cooling to room temperature, this mixture was reduced in (mm, 2H), 1.17 – 0.94 (m, 10H), 0.77 – 0.38 (m, 22H). 13C NMR
volume, and then flash-filtered through alumina (eluent: CCl4). (101 MHz, CDCl3): δ 152.4, 152.2, 151.50, 151.48, 147.4, 146.8,
The filtrate was again concentrated in vacuo to afford a yellow 142.8, 139.9, 138.9, 131.2, 131.0, 130.6, 129.8, 126.2, 126.1,
solid that was added to a mixture of deoxygenated CH2Cl2 and 125.6, 123.9, 123.4, 122.6, 121.2, 120.5, 120.14, 120.12, 118.3,
methanol (1:1, 30 mL), and then K2CO3 (1.85 g, 13.4 mmol) was 91.5, 90.6, 84.3, 82.8, 55.8, 55.4, 39.94, 39.91, 34.8, 31.5, 26.0,
added and the mixture stirred for 6 h. The solvent was removed 25.9, 22.9, 22.9, 22.2, 13.77, 13.75. 11B NMR (128 MHz, CDCl3):
under reduced pressure, and the residue flash-filtered through δ -4.31, -11.10. FT-IR (KBr, cm-1): 2584 (br, B-H); 2200 cm-1 (w,
alumina (eluent: CCl4). Removal of solvent and recrystallization
CºC); 1522, 1341 (s, NO2). HRMS (TOF-MS-ES): Calc. for
from petrol afforded compound 15 as a yellow solid (2.62 g, C50H66B10NO2 ([M – H]+): 822.6024, found 822.6050. Anal. Calcd
7.55 mmol, 85%). 1H NMR (400 MHz, CDCl3): δ 8.29 (dd, J = 8, 2 for C50H67B10NO2: C, 73.95, H7.07, N,1.72. Found: C, 73.74, H,
Hz, 1H), 8.23 (d, J = 2 Hz, 1H), 7.85-7.72 (m, 2H), 7.56 (dd, J = 10, 7.16, N, 1.89.
2 Hz, 2H), 3.24 (s, 1H), 2.07-2.02 (m, 4H), 1.13-1.08 (dd, J = 15,
Synthesis of 2-bromo-7-ethynyl-9,9-di(n-butyl)-9H-fluorene
7 Hz, 4H), 0.71-0.67 (t, J = 7 Hz, 6H), 0.57-0.47 (m, 4H). 13C NMR (18). 7-bromo-9,9-di(n-butyl)-2-iodo-9H-fluorene (3.00 g, 6.21
(101 MHz, CDCl3): δ 152.28, 152.27, 146.6, 139.3, 131.6, 126.8, mmol) in NEt3 (30 mL) was deoxygenated via three freeze-
123.4, 122.7, 121.1, 120.2, 118.3, 84.0, 78.4, 55.7, 39.8, 25.9, pump-thaw cycles, and the flask purged with nitrogen.
22.9, 13.7.
PdCl2(PPh3)2 (130 mg, 0.19 mmol), CuI (70 mg, 0.37 mmol) and
Synthesis
of
2-(n-butyl)-1-(2-((9,9-di(n-butyl)-2-(N,N- trimethylsilylacetylene (0.92 mL, 6.46 mmol) wereadded, and
diphenylamino)-9H-fluoren-7-yl)ethynyl)-9,9-di(n-butyl)-9H-
the mixture stirred at room temperature for 6 h. The solvent
fluoren-7-yl)-1,2-ortho-carborane (16). Compounds 14 (200 was removed under vacuum and the residue was flash-filtered
mg, 0.33 mmol) and 11 (155 mg, 0.33 mmol) were dissolved in through silica column chromatography, eluting with CCl4. The
deoxygenated NEt3/THF (1:1, 40 mL). Pd(PPh3)4 (12 mg, 0.010 solvent was removed to give a yellow solid that was added to a
mmol) and CuI (4 mg, 0.021 mmol) were added and the solution mixture of deoxygenated CH2Cl2 and methanol (1:1, 30 mL).
heated at reflux overnight. The solvent was removed under K2CO3 (1.72 g, 12.42 mmol) was added and the mixture stirred
vacuum, and the residue purified by silica thin-layer for 5 h. The solvent was removed under vacuum, and the
chromatography, eluting with petrol. Removal of solvent and residue flash-filtered through alumina, eluting with petrol.
recrystallization from MeOH/EtOAc afforded compound 16 as a Purification by silica gel column chromatography eluting with
yellow solid (250 mg, 0.26 mmol, 79%). Rf - 0.2 (petrol). 1H NMR petrol/CH2Cl2 (3:1) gave compound 18 as a white solid after
(400 MHz, CDCl3): δ 7.77 – 7.49 (m, 10H), 7.29 (dd, J = 11, 5 Hz, reduction in volume of the solvent (2.04 g, 86%). Rf - 0.50
obscured by CHCl3), 7.21 – 7.13 (m, 5H), 7.11 – 7.01 (m, 3H), (petrol). 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 7.8 Hz, 1H), 7.54
3.40 – 1.50 (br, 10H, B–H and 10H, CH2), 1.46 – 1.32 (m, 2H), (d, J = 8.4 Hz, 1H), 7.47 (t, J = 7.5 Hz, 4H), 3.15 (s, 1H), 2.03-1.86
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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(m, 4H), 1.17-1.02 (m, 4H), 0.68 (t, J = 7.2 Hz, 6H), 0.62-0.49 (m, NMR (400 MHz, CDCl3): δ 7.60-7.54 (m, 4H), 7.45V(idewd,ArJtic=le1O1nl.in8e,
4H). 13C NMR (101 MHz, CDCl3): δ 153.3, 150.4, 140.8, 139.3, 8.1 Hz, 4H), 7.35 (d, J = 8.1 Hz, 2H), 7.25 (d, J = 8.5 Hz, 2H), 4.88-
DOI: 10.1039/C9DT02645B
131.3, 130.2, 126.6, 126.3, 121.7, 121.4, 120.8, 119.7, 84.5, 1.61 (b, 18H, Cage-H and four CH2 (1.83-1.77 (m, 8H)), 1.02-0.86
55.4, 40.0, 25.9, 23.0, 13.8. FT-IR (KBr, cm-1): 3299 (s,
º
CH), 2102 (m, 8H), 0.57 (t, J = 7.3 Hz, 12H), 0.36 (tt, J = 15.5, 7.6 Hz, 4H),
C). HRMS (EI): Calcd. for C23H2579Br: 380.1140, found 0.20 (tt, J = 15.3, 7.5 Hz, 4H). 13C NMR (101 MHz, CDCl3): δ 153.5,
380.1142. Anal. Calcd for C23H25Br: C, 72.44; H, 6.61; Found: C, 150.2, 142.1, 138.9, 136.1, 132.1, 130.0, 129.9, 125.1, 121.9,
72.56; H, 6.58 %.
119.2, 93.9, 86.4, 55.3, 39.6, 25.7, 22.8, 13.8. 11B NMR: (128
Synthesis of 1,2-bis(2-bromo-9,9-di(n-butyl)-9H-fluoren-7- MHz, CDCl3): δ -2.83, -10.79. FT-IR (KBr, cm-1): 2643-2592 (br, B-
yl)ethyne (19). Compound 18 (1.14 g, 3.00 mmol) and 7-bromo- H). HRMS (TOF-ES): Calcd. for C44H57B10I2
[M - H]+): 949.3480,
(w, C
º
(
9,9-di(n-butyl)-2-iodo-9H-fluorene (1.45 g, 3.00 mmol) were found 949.3481. Anal. Calcd for C44H58B10I2 (%): C, 55.70; H,
added to deoxygenated NEt3/THF (1:1, 40 mL). PdCl2(PPh3)2 6.16. Found: C, 55.67; H, 6.19.
(105 mg, 0.15 mmol) and CuI (60 mg, 0.3 mmol) were added and
Synthesis
of
1,2-bis(2-((9,9-di(n-butyl)-2-(N,N-
the solution heated at reflux overnight. The reaction was diphenylamino)-9H-fluoren-7-yl)ethynyl)-9,9-di(n-butyl)-9H-
allowed to cool, and the solvent was then removed under fluoren-7-yl)-1,2-ortho-carborane (22). Compounds 21 (200
vacuum, and the residue passed through a short pad of silica, mg, 0.21 mmol) and 11 (200 mg, 0.42 mmol) were dissolved in
eluting with petrol. The solvent was removed under vacuum, a mixture of NEt3 and THF (1:1, 30 mL). Pd(PPh3)4 (12 mg, 0.01
and the residue purified by silica column chromatography, mmol) and CuI (4 mg, 0.02 mmol) were added and the solution
eluting with petrol. The solvent was reduced in volume to give heated at reflux overnight. The solvent was removed under
a white solid identified as compound 19 (1.67 g, 2.27 mmol, vacuum and the residue purified by silica thin-layer
1
76%). Rf -0.6 (petrol). H NMR (400 MHz, CDCl3): δ 7.69 (d, J = chromatography, eluting with petrol. Removal of solvent and
7.8 Hz, 2H), 7.58 (dd, J = 8.0, 6.0 Hz, 6H), 7.50 (d, J = 6.7 Hz, 4H), recrystallization from MeOH/CH2Cl2 afforded a yellow solid
2.00 (h, J = 13.5 Hz, 8H), 1.18-1.07 (m, 8H), 0.72 (t, J = 7.3 Hz, identified as 22 (267 mg, 0.162 mmol, 65%). Rf -0.3 (petrol). 1H
12H), 0.67-0.54 (m, 8H). 13C NMR (101 MHz, CDCl3): δ 153.2, NMR (400 MHz, CDCl3) : δ 7.70-7.36 (m, 20H), 7.26 (t, J = 6.9 Hz,
150.5, 140.3, 139.5, 130.8, 130.2, 126.2, 125.9, 122.0, 121.6, 9H), 7.13 (d, J = 8.1 Hz, 9H), 7.03 (d, J = 6.3 Hz, 6H), 4.11-1.61
121.3, 119.8, 90.7, 55.4, 40.2, 25.9, 23.0, 13.8. FT-IR (KBr, cm-1): (m, 26H, Cage-H and eight CH2 (1.88, m, 16H)), 1.03 (dd, J = 38.8,
2162 (w, C
found 734.2122. Anal. Calcd for C44H48Br2: C, 71.74; H, 6.57; NMR (101 MHz, CDCl3): δ 152.5, 151.3, 151.1, 150.7, 147.9,
Found: C, 71.64; H, 6.69 %. 147.7, 142.5, 141.4, 139.3, 135.4, 130.74, 130.69, 123.0, 129.7,
º
C). HRMS (EI): Calcd. for C44H4879Br2: 734.2123, 4.8 Hz, 16H), 0.82-0.50 (m, 32H), 0.40 (s, 4H), 0.24 (s, 4H). 13C
Synthesis of 1,2-bis(2-iodo-9,9-di(n-butyl)-9H-fluoren-7- 129.2, 125.9, 125.8, 125.2, 124.0, 123.3, 122.9, 122.7, 120.7,
yl)ethyne (20). Compound 19 (1.00 g, 1.36 mmol) was added to 120.4, 120.3, 119.3, 119.0, 119.0, 91.4, 90.0, 86.6, 55.2, 55.0,
THF (20 mL) and the solution was cooled to -78 °C. n-BuLi (3.6 40.0, 39.9, 26.0, 25.8, 23.0, 22.9, 13.9, 13.8. 11B NMR (128 MHz,
mL, 1.6 M solution in hexane, 5.76 mmol) was slowly added via CDCl3): δ -3.91, -10.91. FT-IR (KBr, cm-1): 2589 (br, B-H), 2197 (w,
syringe, and the mixture stirred for 2 h. Iodine (414 mg, 3.26
CºC). MS (MALDI-TOF): m/z calcd for C114H126B10N2: 1632.0948,
mmol) in THF (20 mL) was added and the mixture warmed to RT found 1632.0927. Anal. Calcd for C114H126B10N2: C, 83.88; H,
and left to stir for 30 min. The mixture was washed with 7.78; N, 1.72. Found: C, 83.93; H, 7.75; N, 1.69.
aqueous Na2S2O3 and extracted with CH2Cl2. The organic layer
was dried with MgSO4 and the solvent removed under vacuum.
Conclusions
The residue was then passed through a short pad of alumina,
eluting with petrol, and the solvent reduced in volume to give a
white solid identified as 20 (0.78 g, 0.94 mmol, 69%). Rf - 0.6
Displacement of the Lewis bases from B10H12(SEt2)2 has afforded
a range of C-functionalized o-carboranes in fair to good yields,
the products being subjected to spectroscopic and in most cases
single-crystal X-ray structural study. Quadratic optical
nonlinearities were assessed by hyper-Rayleigh scattering using
ns pulsed radiation at a measurement wavelength of 1064 nm,
and therefore corresponding to a second-harmonic wavelength
of 532 nm at which all compounds are optically transparent. The
NLO studies confirmed that, as expected, replacing the terminal
phenyl group by an electron-withdrawing o-carborane unit
results in a significant increase in quadratic nonlinearity,
introduction of weakly electron-donating phenyl or n-butyl
groups results in a small decrease in nonlinearity, replacement
of the electron-donating diphenylamino group by an electron-
withdrawing nitro group (and thereby progressing from a D-B-A
assembly to an A-B-A construction) leads to a significant
decrease in nonlinearity, and replacement of the 1,4-phenylene
bridge unit by 9,9-di-n-butyl-2,7-fluorenylene groups results in
a doubling or greater of the quadratic NLO coefficient.
1
(petrol). H NMR (400 MHz, CDCl3) δ 7.71 (t, J = 10.8 Hz, 4H),
7.60 (d, J = 7.8 Hz, 4H), 7.37 (d, J = 4.9 Hz, 4H), 2.03 (t, J = 8.2 Hz,
8H), 1.16-1.08 (m, 8H), 0.71 (t, J = 7.2 Hz, 12H), 0.68-0.55 (m,
8H). 13C NMR (101 MHz, CDCl3): δ 151.0, 150.8, 141.4, 140.5,
130.6, 127.5, 126.9, 125.9, 122.9, 121.6, 120.0, 119.7, 90.5,
55.1, 40.3, 25.9, 23.1, 13.8. FT-IR (KBr, cm-1): 2162(w, C
ºC).
HRMS (TOF-ES): Calcd. for C44H48I2: 830.1846, found 830.1846.
Synthesis of 1,2-bis(2-iodo-9,9-di(n-butyl)-9H-fluoren-7-yl)-
1,2-ortho-carborane (21). Compound 20 (0.50 g, 0.60 mmol)
and B10H12(SEt2)2 (0.27g, 0.90 mmol) in dry toluene (20 mL) was
heated at reflux for 3 days. The mixture was cooled to room
temperature and MeOH (20 mL) was added to quench the
reaction. The solvent was removed by evaporation under
vacuum, and the residue was filtered through a short pad of
alumina, eluting with toluene. Purification by silica plate
chromatography, eluting with petrol, gave a white solid
1
identified as 21 (0.21 g, 0.22 mmol, 37%). Rf -0.5 (petrol). H
8 | J. Name., 2012, 00, 1-3
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ARTICLE
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View Article Online
DOI: 10.1039/C9DT02645B
b
2816.
significant increase given the unfavourable alignment of these
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There are no conflicts of interest to declare.
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Acknowledgements
We thank the Program of Introducing Talents of Discipline to
Universities (111 Project B13025), the Fundamental Research
Funds for the Central Universities (JUSRP11423), the Natural
Science Foundation of Jiangsu Province, China (No.
BK20140140), the National Natural Science Foundation of China
(No. 21502072), and the Australian Research Council
(DP170100411) for support.
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DOI: 10.1039/C9DT02645B
Electron-withdrawing o-carboranes C-functionalized by one 2-donor-7-fluorenyl
unit are shown to exhibit strong quadratic optical nonlinearities at 1064 nm;
appending two donor-functionalized fluorenyl groups further enhances the NLO
coefficients.