Synthesis, structure and density functional theory calculations of a novel photoluminescent trisarylborane–bismuth(III) complex

Article abstract of DOI:10.1002/bio.3667

A novel trisarylborane–Bi(III) complex, tris(4-(dimesitylboryl)phenyl)bismuthine [Bi(PhBMes₂)₃], in which (Ph?=?phenyl, and Mes?=?mesityl), was synthesized via the reaction of bismuth (III) chloride (BiCl₃) with three equi

Full text of DOI:10.1002/bio.3667

Received: 29 March 2019
DOI: 10.1002/bio.3667
Revised: 12 May 2019
Accepted: 28 May 2019
R E S E A R C H A R T I C L E
Synthesis, structure and density functional theory calculations
of a novel photoluminescent trisarylborane–bismuth(III)
complex
1
1
2
|
|
Hazem Amarne
Wissam Helal
Suning Wang
1
Department of Chemistry, The University of
Jordan, Amman, Jordan
Abstract
2
Department of Chemistry, Queen's
A
novel trisarylborane–Bi(III) complex, tris(4‐(dimesitylboryl)phenyl)bismuthine
Bi(PhBMes ], in which (Ph = phenyl, and Mes = mesityl), was synthesized via the
reaction of bismuth (III) chloride (BiCl ) with three equivalents of lithiated (4‐
University, Kingston, Ontario, Canada
[
2 3
)
Correspondence
3
Hazem Amarne, Department of Chemistry, The
University of Jordan, Amman 11942, Jordan.
Email: h.amarne@ju.edu.jo
bromophenyl)‐ dimesitylborane [BrPhBMes ]. The new trisarylbismuthine was char-
2
acterized by elemental analysis, ultraviolet–visible (UV–vis) spectroscopy, and NMR
1
13
(
H and C) spectroscopy. The molecular structure of Bi(PhBMes ) in the solid state
2 3
Funding information
Deanship of Academic Research, University of
Jordan; Natural Sciences and Engineering
Research Council of Canada
was determined using single‐crystal X‐ray diffraction analysis, which showed short
intermolecular C–H···H–C contact. The complex is fluorescent emitter
max = 395 nm) at room temperature and a phosphorescent emitter (λmax = 423 nm)
a
(
λ
at 77 K, which displayed a long lifetime of 495 ms. The UV–vis transitions were inves-
tigated using density function theory (DFT) and time‐dependent (TD)‐DFT
calculations. Natural bond orbital analysis showed that the bismuth (III) center was
mainly Lewis acidic in nature.
KEYWORDS
charge transfer, DFT calculations, Lewis acidic Bi(III) complex, photoluminescence, tri‐coordinate
organoboron complex
1
|
INTRODUCTION
with a perpendicular empty p orbital that leads to strong conjugation
with adjacent π systems and also provides a platform for selective
[
6]
Luminescent organometallic compounds have been widely studied
and sensitive chemical sensing. Although the Lewis acid characteris-
tics of tri‐coordiante organoborons have a negative effect on their
chemical stability, the boron center can be protected by sterically
demanding substituents such as mesityl groups. These protecting
groups provide kinetic stability without affecting the characteristic
features of the boron center.
[
1]
mainly due to their potential for use in biological applications,
[
2]
chemical sensing, and as efficient light‐emitting materials in organic
[3]
light‐emitting diodes (OLEDs). Their efficiency comes from the
promotion of singlet‐triplet state mixing, which can highly improve
luminescence efficiency. This singlet‐triplet state mixing can be pro-
moted by spin‐orbit coupling, which can be highly induced via heavy
The incorporation of a heavy metal complex into tri‐coordinate
organoboron compounds can induce phosphorescence and eventually,
when the compound is used in OLEDs, higher efficiency is expected
because both singlet and triplet excitons can be utilized. Also, the
presence of the boron empty p orbital can stabilize the metal‐to‐ligand
charge‐transfer (MLCT) state and consequently enhance phosphores-
cence. Recently, many luminescent compounds incorporating both
[
4]
metals. Luminescent organometallic compounds based on heavy
transition and main group metals e.g. Pt(II), and Ir(III) are of particular
interest as they exhibit large heavy atom effects.
Conversely, tri‐coordinate organoboron compounds have attracted
[
5]
much attention because of their rich optoelectronic properties. The
interest in these compounds stems from their trigonal planar geometry
Luminescence. 2019;1–8.
wileyonlinelibrary.com/journal/bio
© 2019 John Wiley & Sons, Ltd.
1

2
AMARNE ET AL.
heavy transition/main group metals and triaryl boron substituents
After filtrating out the salts, solvents were removed under reduced
pressure and the residue was purified over silica gel using a gradient
[7]
[8]
[9]
[10]
have been studied, including Pt(II),
Ir(III),
Ru(II),
Re(I),
[
11]
[12]
[13]
Cu(I),
Zn(II),
and Hg(II),
[15]
in addition to other main group
of a hexanes/CH
lized from CH Cl
NMR (CD Cl
2
Cl
2
mixture. The resulting white solid was recrystal-
[
14]
1
metals
including Bi(III).
2
2
/hexanes to give colorless crystals (yield: 26%).
H
Nonetheless, Bi(III)‐based luminescent organometallic compounds
2
2
, δ, ppm): 7.73 (2H, d, J = 8.0 Hz), 7.43 (2H, d,
[
16]
13
remain scarce
and the main focus on tri‐arylbismuth (III)
2 2
J = 7.6 Hz), 6.80 (4H, s), 2.28 (6H, s), 1.96 (12H, s). C NMR (CD Cl ,
compounds has been for their use as catalysts in different organic
δ, ppm): 161.7, 145.7, 142.0, 141.1, 139.0, 138.0, 137.4, 128.5, 23.5,
[
17]
transformations,
which is mainly achievable via the Lewis acid
78 3
21.3. Anal. Calcd. (%) for C72H B Bi: C, 72.99; H, 6.64. Found: C,
characteristics of Bi(III) compounds. The latter is a result of the
relativistic contraction of the valance 6s orbital, which lowers its
energy and hence lowers the tendency of the lone pair to participate
72.76; H, 6.81.
−
1
−1
UV–vis (CH
2 2
Cl ) [λmax (nm), ε (M .cm )]: (232, 72,353); (262,
34,439); (270, 35,936); (322, 56,685).
[
18]
as a Lewis base.
In addition, Bi(III) compounds in general have
relatively low toxicity and hence they have been used in several
[
19]
biological applications.
2.3
|
Theoretical calculations
Here we report the synthesis and characterization of a novel Bi(III)
complex functionalized with trisaryl organoboron moieties; this paper
describes is the first published example of a trisarylbismuthine con-
nected to a boron center via an aromatic ring. The structure and the
photophysical properties of the new compound are reported.
All quantum mechanical calculations were performed using the Gauss-
[
21]
ian 09 program package.
2 3
The crystal structure of Bi(PhBMes ) was
used as the starting point for geometry optimization. The molecular
structure was optimized at the density function theory (DFT) level of
theory using the Becke, 3‐parameter, Lee–Yang–Parr (B3LYP) func-
tional, in which the LANL2DZ basis set was used for the bismuth atom
and the 6‐31G(d) basis set was used for all other atoms. Frequency
calculations were carried out for the optimized geometry of the com-
plex at the same level of theory to check if the optimized geometry
obtained was a true global minimum.
2
2
|
EXPERIMENTAL
.1
|
General considerations
All experiments were carried out under an atmosphere of dry nitrogen
using standard Schlenk techniques or in glove box. 1,4‐
Dibromobenzene, n‐BuLi, BMes F and BiCl were purchased from
To assign the main bands in the absorption spectrum of the com-
plex, the lowest six, 20 and 50 singlet‐singlet excited states were cal-
culated for the optimized geometry, using time‐dependent DFT (TD‐
DFT). It was found that a large window of the lowest 50 excited states
would be needed to cover the whole required experimental spectrum
range. Three different hybrid functionals were used in TD‐DFT calcu-
lations, namely: B3LYP, CAM‐B3LYP and PBE0, with the same basis
set used for the geometry optimization.
a
2
3
Aldrich chemical company and used without further purification.
Solvents were purchased from Aldrich chemical company and were
dried using an activated alumina column system, purchased from
Innovative Technology Inc. Thin‐layer chromatography and flash
1
13
chromatography were performed on silica gel. H and C NMR
spectra were recorded on Bruker Avance 400 or 500 MHz
spectrometers. Deuterated solvents were purchased from Cambridge
Isotopes and used as received. UV–vis spectra were recorded on an
Ocean Optics Model CHEMUSB4 UV–vis spectrometer. Excitation
and emission spectra were recorded on a Photon Technologies Inter-
national QuantaMaster Model C‐60 spectrometer. Elemental analysis
was performed by the Analytical Laboratory for Environmental
Science Research and Training (ANALEST; Department of Chemistry,
2 2
In addition, the solvation effect of dichloromethane (CH Cl ) was
accounted for using the polarizable continuum model (CPCM) in all
TD‐DFT calculations. UV–vis plots and analysis were performed using
[22]
the GaussSum 3.0 program.
Natural bond orbital (NBO) analysis
was performed using the NBO 3.1 program implemented in
[23]
Gaussian.
8
0 St. George Street, University of Toronto, Toronto, Ontario, Canada
2
.4
|
X‐ray crystallographic analysis
M5S 3H6). BrPhBMes was synthesized based on a previously
2
[
20]
published procedure.
Single crystals of the Bi(PhBMes
CH Cl /hexanes. Crystals were mounted on a glass fiber and data
collection was carried out on a Bruker Apex II single‐crystal X‐ray
diffractometer, with graphite‐monochromated MoK radiation
operating at 50 kV and 35 mA. Data were processed using the Bruker
2 3
) complex were obtained from
2
2
2
.2
|
Synthesis of the Bi(PhBMes ) complex
2 3
α
To a solution of BrPhBMes
78°C, n‐BuLi (1.6 M in hexane, 0.56 ml, 0.9 mmol) was added slowly
and mixed for 60 min at −78°C. The resulting solution was transferred
to a dry Et O (20 ml) solution of BiCl (0.09 g, 0.3 mmol) via a cannula
2 2
(0.37 g, 0.9 mmol) in dry Et O (30 ml), at
[
24]
−
SHELXTL software package
and corrected for absorption effects
and the structure was solved by direct methods. All non‐hydrogen
atoms were refined anisotropically. The positions of hydrogen atoms
were calculated, and their contributions in structural factor calcula-
tions were included.
2
3
at −78°C. The resulting solution was stirred for 1 h at −78°C, then it
was allowed to warm to ambient temperature and stirred overnight.

AMARNE ET AL.
3
Crystallographic data for Bi(PhBMes
Table S1.
2 3
The reported crystallographic data for Bi(PhBMes ) have been
2 3
) complex are summarized in
deposited with the Cambridge Crystallographic Data Centre (Deposi-
tion No. CCDC 1,588,775). The data can be obtained free of charge
via https://www.ccdc.cam.ac.uk/structures/, or by emailing:
data_request@ccdc.cam.ac.uk, or by contacting the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK;
Fax: +44 1223 336033.
Hirshfeld surface analysis was performed using the CrystalExplorer
[
25]
3
.1 program.
FIGURE 1 UV–vis absorption and photoluminescence spectra of
3
3
|
RESULTS AND DISCUSSION
Synthesis and characterization
Bi(PhBMes2)3 in dichloromethane at room temperature
.1
|
a different type of LLCT (4) a shoulder at (λmax = 262 nm;
−1
−1
ε = 34,439 M .cm ) which might be partially attributed to an MLCT
Synthesis of Bi(PhBMes
Scheme 1, in which an Et
equivalents of LiPhBMes , and purified on silica gel using flash chro-
matography. The pure compound was crystallized by slow evaporation
of hexanes into a CH Cl solution to furnish colorless crystals with a
6% yield. The complex was characterized by H and C NMR spec-
2
)
3
: The complex was prepared according to
from the lone pair of electrons on bismuth to the phenyl rings
2
O solution of BiCl was added to three
3
(
n→π*ph) and the empty p orbitals on boron atoms (see Section 3.3
below for band assignments using TD‐DFT).
Generally, BiAr compounds have absorption bands originating
2
3
2
2
from ligand‐based transitions (π→π*) in addition to an n→π* shoulder
[16]
1
13
2
band that sometimes gets hindered by the other peaks.
Also, BAr
3
troscopy, elemental analysis and single‐crystal X‐ray diffraction.
The molecular structure was unambiguously established by single‐
crystal X‐ray diffraction. In addition, the formation of a Bi–C (ipso)
compounds, in which two of the aromatic rings are mesityl, are known
to have ligand‐based transitions (π→π*) with one of the bands being a
[5,7–9]
Mes→B empty p‐orbital transition.
In this regard, our compound
13
bond was also confirmed by the presence of the C NMR peak
would have all these features combined, in addition to the MLCT orig-
around 162 ppm and the disappearance of the Br–C (ipso) peak
inating from the Bi lone pair → B empty p orbit. Also, the absorption
13
around 127 ppm. The strong C NMR down‐field shift might be
maxima and molar extinction coefficients in Bi(PhBMes
rable with those of similarly substituted BiAr and BAr
When excited with UV light at 335 nm, at ambient temperature,
Bi(PhBMes (in CH Cl ) displayed a broad fluorescent (green emis-
sion) band (350–600 nm) with a λmax = 395 nm (Figure 1). Conversely,
upon cooling to 77 K the CH Cl frozen solution displayed an intense
2
)
3
are compa-
[26]
attributed to spin‐orbit coupling caused by bismuth.
3
3
compounds.
|
Photophysical properties
2
)
3
2
2
3
.2
The UV–vis absorption of Bi(PhBMes
2
)
3
was measured in CH
2
Cl
2
. The
2
2
spectrum, shown in Figure 1, reveals three strong absorption bands
emission (greenish‐blue) band at λmax = 423 nm (Figure S1), which was
attributed to phosphorescence because of the associated long decay
lifetime (Figure S2), [495 ms (63%) and 2111 ms (37%)].
−1
−1
and a shoulder: (1) a band at (λmax = 232 nm; ε = 72,353 M .cm
)
which might be attributed to ligand‐to‐ligand charge transfer (LLCT)
−
1
−1
(
2) a band at (λmax = 270 nm; ε = 35,936 M .cm ) which might be
attributed to phenyl‐based π–π* transitions (3) band at
max = 322 nm; ε = 56,685 M .cm ), which might be attributed to
3
The fluorescence of Mes‐substituted BAr compounds, has been
a
largely attributed to a LLCT process that involved one of the Mes
−
1
−1
[5,7–9]
(
λ
groups and the
B
empty
p
orbit
;
based on the
2 3
SCHEME 1 Synthetic route to the Bi(PhBMes ) complex

4
AMARNE ET AL.
absorption/emission spectra and TD‐DFT calculations this is believed
to be the case for our compound. Conversely, the phosphorescence
peak from our compound was most probably due to the heavy atom
and dihedral angles were also reasonably comparable with that of
the solid‐state geometry.
Isosurface densities for some of the frontier occupied and unoccu-
pied molecular orbitals involved in the UV–vis transitions of the
effect caused by the Bi center; this effect is very well known in BiAr
3
[
16]
complexes.
2 3
Bi(PhBMes ) complex are depicted in Figure S4. The first three low-
est unoccupied molecular orbitals (LUMOs) LUMO+1, and LUMO+2,
have mainly boron characteristics (empty p orbitals), in addition to
some π* characteristics of the orbitals delocalized over the phenyl
rings. Conversely, the highest occupied molecular orbitals (HOMOs)
are mainly localized on the mesityl rings with some phenyl rings
contribution. Also, of particular interest is the HOMO‐18 orbital,
3
.3
|
DFT and TD‐DFT calculations
The optimized geometry at the B3LYP/6‐31 g(d) + LANL2DZ level is
shown in Figure S3. Selected calculated geometrical parameters of
the optimized geometry of the complex are summarized in Table 1,
together with corresponding experimental X‐ray results. Different cal-
culated parameters of the complex are in good agreement with the
corresponding X‐ray data. Most of the calculated bond lengths were
less than 0.01 Å and deviated from the corresponding bonds obtained
from the solid‐state structure, except Bi(1)–C(1) and C(4)–B(1) in
which the deviation was around 0.015 Å. Also, the calculated angles
2
which has a Bi 6s lone pair characteristic, a Bi–C σ‐characteristic,
and a π‐characteristic from the phenyl rings.
The simulated UV–vis spectra obtained from TD‐DFT calculations,
based on the three different functionals, along with the experimental
one are combined in Figure 2. The spectrum obtained based on
B3LYP functional revealed only two major bands at 340 nm and
276 nm. Similarly, two major bands at 332 nm and 269 nm were
obtained when the hybrid PBE0 functional was used. Conversely,
the simulated UV–vis spectrum obtained using the CAM‐B3LYP was
a much better fit, in which three major bands appeared around
TABLE 1 Selected bond distances (Å), angles (°), and dihedral angles
°) for the Bi(PhBMes
(
2 3
) complex obtained by X‐ray and DFT calcula-
296 nm, 260 nm, and 220 nm. The main measured UV–vis bands
tions [B3LYP/6‐31G(d) + LANL2DZ]
and the simulated bands obtained from the CAM‐B3LYP functional
are summarized in Table 2. The detailed calculated transition bands
using CAM‐B3LYP functional are reported in Table S2.
X‐ray
Calculated
Bond length (Å)
Bi(1)–C(1)
2.252(3)
2.257(2)
2.264(3)
1.555(4)
1.566(4)
1.574(4)
1.581(4)
1.580(4)
1.582(5)
2.24876
2.24891
2.24890
1.57252
1.57116
1.57252
1.58554
1.58453
1.58484
Considering the major contribution of the electronic bands com-
puted by TD‐DFT, the band at λmax = 232 nm could be assigned to a
LLCT from the conjugated π system (mesityl and phenyl) to the empty
boron orbitals and the π* of the phenyl ring. Also, the band at
Bi(1)–C(25)
Bi(1)–C(49)
C(4)–B(1)
λmax = 270 nm could be assigned to another LLCT from the phenyl π
C(28)–B(2)
orbitals to the phenyl π* and empty boron orbitals transitions. In addi-
tion, the transitions corresponding to the band at λmax = 322 nm could
be assigned to a different LLCT from the mesityl π orbitals to the phe-
nyl π* and empty boron orbitals. Finally, the shoulder at λmax = 262 nm
could be partially attributed to an MLCT from the bismuth lone pair to
the phenyl rings (n→π*ph) and the boron empty p orbitals.
C(52)–B(3)
C(21)–B(1)
C(40)–B(2)
C(55)–B(3)
Angle (°)
C(1)–Bi(1)–C(25)
C(1)–Bi(1)–C(49)
C(25)–Bi(1)–C(49)
Dihedral angle (°)
C(1)–Bi(1)–C(49)–C(50)
C(1)–Bi(1)–C(25)–C(26)
Bi(1)–C(1)–C(2)–C(3)
Bi(1)–C(25)–C(26)–C(27)
Bi(1)–C(49)–C(50)–C(51)
C(2)–C(3)–C(4)–B(1)
C(26)–C(27)–C(28)–B(2)
C(50)–C(51)–C(52)–B(3)
C(3)–C(4)–B(1)–C(21)
C(27)–C(28)–B(2)–C(40)
C(51)–C(52)–B(3)–C(55)
93.43(9)
94.17(9)
93.22(9)
96.924
95.942
95.765
Population analysis using the NBO regime revealed a value of the
calculated natural charge on the Bi atom of +1.22 (Table S3).
14.410
97.383
11.484
96.340
175.991
178.589
178.228
171.717
178.454
176.284
21.545
178.636
179.858
178.865
179.403
179.06
179.322
23.233
24.843
25.997
FIGURE 2 Combined UV–vis absorption spectra, experimental vs
simulated, of Bi(PhBMes )
2 3
19.315
24.167

AMARNE ET AL.
5
TABLE 2 The strongest UV–vis absorption bands of the
2 3
Bi(PhBMes ) complex from TD‐DFT calculations [B3LYP/6‐
3
1G(d) + LANL2DZ/CPCM (DCM)] and experiment in DCM solvent
Calculated
Experimental
max (nm)
322
λ
max
Oscillator
strength
(
nm)
Major contributions
λ
2
95.56 0.5132
HOMO‐5 → LUMO (0.363),
HOMO‐5 → LUMO+2 (0.302),
HOMO → LUMO (0.282)
2
2
2
94.39 0.5081
59.98 0.1770
59.43 0.1357
HOMO‐4 → LUMO+2 (0.369),
HOMO → LUMO+1 (0.314)
HOMO‐13 → LUMO+2 (0.255), 270
HOMO‐9 → LUMO+1 (0.235)
FIGURE 3 Molecular structure of the Bi(PhBMes
selected bond lengths (Å) and angles (°): Bi(1)–C(1) 2.252(3), Bi(1)–
C(25) 2.257(2), Bi(1)–C(49) 2.264(3), C(4)–B(1) 1.555(4), C(7)–B(1)
2
)
3
complex with
HOMO‐17 → LUMO+1 (0.292),
HOMO‐14 → LUMO+2 (0.292)
1
.586(4), C(21)–B(1) 1.581(4), C(28)–B(2) 1.566(4), C(31)–B(2)
1.577(4), C(40)–B(2) 1.580(4), C(52)–B(3) 1.574(4), C(55)–B(3)
.582(5), C(69)–B(3) 1.577(5); C(1)–Bi(1)–C(25) 93.43(9), C(1)–Bi(1)–
2
2
46.02 0.2113
45.61 0.235
HOMO‐18 → LUMO (0.337)
262 (shoulder)
1
HOMO‐18 → LUMO+1 (0.349),
HOMO‐15 → LUMO+2 (0.236)
C(49) 94.17(9), C(25)–Bi(1)–C(49) 93.22(9), C(4)–B(1)–C(21) 118.8(2),
C(4)–B(1)–C(7) 117.6(2), C(21)–B(1)–C(7) 123.6(2), C(28)–B(2)–C(31)
2
2
20.75 0.1882
20.25 0.1262
HOMO‐21 → LUMO (0.227),
HOMO‐19 → LUMO (0.186)
232
119.4(2), C(28)–B(2)–C(40) 119.7(2), C(31)–B(2)–C(40) 120.9(2),
C(52)–B(3)–C(69) 115.4(3), C(52)–B(3)–C(55) 120.9(3), C(69)–B(3)–
C(55) 123.6(3)
HOMO‐23 → LUMO+1 (0.175),
HOMO‐20 → LUMO+2 (0.194)
Compared with the +3 formal charge on Bi(III), an electron density of
around two negative charges was ‘transferred’ from the ligands to
the bismuth metal center, which implies a Lewis acid characteristic
of the Bi center. Also, the natural electron configuration of Bi is [core]
important bond lengths and angles are shown in Figure 3. Crystal data
and structure refinement of the complex can be found inTable S1. The
Bi(III) central atom adopted a distorted trigonal pyramidal geometry
and the three ligands (legs) around it were arranged in a propeller‐like
shape. Similarly, the three aromatic rings around each boron form pro-
pellers themselves, which could be expected when the substituents
6
s(1.71) 6p(2.05) (Table S3). Therefore, it can be concluded that the
charge transferred to Bi is located on the three 6p orbitals. In addition,
the lone pair of electrons on Bi is mainly has s characteristics (about
[
16]
around Bi or B are sterically demanding.
8
2
0%) (Figure S5), but there is a significant p characteristic (about
The Bi–C bond lengths of 2.252(3) Å, 2.257(2) Å and 2.264(3) Å
and the C‐Bi‐C bond angles of 93.22(9)°, 93.43(9)° and 94.17(9)° were
2
0%) participating in the hybridization of the 6s lone pair orbital, as
can be deduced from NBO analysis (Table S4).
all within the reported range for related Bi(Ar)
Bi–C bond length in BiPh is 2.237–2.273 Å, and 2.31–2.32 Å) in
Also, the sum of bond angles around the Bi center was
about 281°, which is very similar to BiPh (282°), but smaller than that
of the more sterically demanding BiMes (308°). Also, this relatively
3
compounds, e.g. the
The second order perturbation theory analysis of the Fock matrix
in NBO basis identified a [LP Bi(1) → BD* C(25)–C(26)] donor–
acceptor interaction (LP = lone pair and BD = 2‐center bond), a
3
[
16,27]
BiMes3.
3
[
BD C(25)–C(26) → BD* C(27)–C(28)], and a [BD C(27)–C(28) →
3
LP* B(2)] (Figure S5 and Table S5). This interaction was also
observed in corresponding adjacent carbon and boron atoms on
small bond angles sum around Bi center supports the large s character-
istic of the Bi lone pair discussed earlier that partially contributed to
the stability of the compound.
2
the other two legs of the ligand. The donation of the Bi 6s lone pair
to the adjacent C–C bonds contributed to the stability of the mole-
The B–Cph bond lengths of 1.555(4) Å, 1.566(4) Å and 1.574(4) Å,
the B–CMes bond lengths of 1.586(4) Å, 1.581(4) Å, 1.577(4) Å,
1.580(4) Å, 1.582(5) Å and 1.577(5) Å, and the C–B–C bond angles
of 118.8(2)°, 117.6(2)°, 123.6(2)°, 119.4(2)°, 119.7(2)°, 120.9(2)°,
115.4(3)°, 120.9(3)° and 123.6(3)° are all within the reported range
cule by about 1.2 kcal/mol, while the contribution of each of the
other two donor–acceptor interactions was about 20 kcal/mol
2
(
Table S5). This observation indicated that the Bi 6s lone pair was
acting as a Lewis base in addition to the fact that its 6p orbitals
were Lewis acidic in nature.
[
5,7,8]
for related BAr
compound are all planar with the sum of the C–B–C bond angles equal
to 360°, which is similar to other B centers in BAr compounds with
3
compounds.
Also, the three B centers in our
3
[
5,7,8]
3
.4
|
Crystal structure
two mesityl rings.
2
The high s characteristic of the 6s lone pair and the trigonal pyra-
2 3
The solid‐state structure of the Bi(PhBMes ) complex was unambigu-
midal geometry around Bi, which dictates a hemidirected arrangement
2
ously determined by X‐ray diffraction analysis. Oak Ridge thermal
of ligands around the central Bi ion, strongly suggested that the 6s
[
28]
ellipsoid plot (ORTEP) drawings of the complex along with a list of
lone pair is stereochemically active.

6
AMARNE ET AL.
The crystal structure packing of Bi(PhBMes
a short intermolecular C–H···H–C distance of 2.341 Å, between
phenyl–H and one of the mesityl CH hydrogens, which is less than
the sum of van der Waals radii of 2.40 Å.
CH hydrogens interacted in a similar fashion with the phenyl carbon
atoms (2.885 Å) and with the aromatic mesityl carbon atoms (2.825–
.874 Å); in both cases the C–H···C–C intermolecular distances were
2
)
3
(Figure S6) revealed
order perturbation analysis shows a donor–acceptor interaction
2
between the Bi(III) 6s lone pair and the empty p orbital on boron
3
through the phenyl conjugated system.
[29]
In addition, the mesityl
3
ACKNOWLEDGMENTS
We thank the Natural Sciences and Engineering Research Council of
Canada and the Deanship of Academic Research, University of Jordan
for financial support.
2
less than the sum of van der Waals radii of 2.97 Å.
These H···H and H···C short interactions are not very uncommon in
compounds with sterically demanding groups, mainly because these
bulky groups are highly polarizable and hence can engage in London
dispersion (LD) interactions. In many cases, these LD interactions are
more favorable than the repulsion forces caused by the bulky groups,
DISCLOSURE STATEMENT
No potential conflict of interest was reported by the authors.
[
30]
leading to short intermolecular interactions.
Also, these interactions
in the solid
ORCID
seemed to be contributing to the stability of Bi(PhBMes )
2 3
Hazem Amarne https://orcid.org/0000-0003-3976-5521
state and hence, the stability toward elution through silica gel.
Conversely, our compound did not have any Bi–π interactions
REFERENCES
(
Menshutkin‐type interactions) nor did it have π–π interactions, which
[
1] (a) Q. Zhao, C. Huang, F. Li, Chem. Soc. Rev. 2011, 40, 2508; (b) K. K.
W. Lo, Acc. Chem. Res. 2015, 48, 2985; (c) S. S. Pasha, P. Das, N. P.
Rath, D. Bandyopadhyay, N. R. Jana, I. R. Laskar, Inorg. Chem. Commun.
have been reported to promote aggregation and emission from
excimer species.
2
016, 67, 107; (d) Q. Zhao, M. Yu, L. Shi, S. Liu, C. Li, M. Shi, Z. Zhou,
The above‐mentioned intermolecular interactions were also con-
firmed via Hirshfeld surface analysis. Packing diagrams showing short
H···H and H···C contacts with distance of 2.166 and 2.383 Å and
C. Huang, F. Li, Organometallics 2010, 29, 1085; (e) R. W. Y. Sun, A. L.
F. Chow, X. H. Li, J. J. Yan, S. S. Y. Chui, C. M. Che, Chem. Sci. 2011, 2,
7
28; (f) S. K. Fung, T. Zou, B. Cao, T. Chen, W.‐P. To, C. Yang, C.‐N.
2
.713 and 2.904 Å, respectively, are shown in Figures S7 and S8. Also,
Lok, C.‐M. Che, Nat. Commun. 2016, 7, 10655.
the generated fingerprint plot (Figure S9), represented by spikes, show
the H···H (red circle) and H···C (black circles) interactions, in which
H···H contacts contributed to 80.2% of the surface and H···C contacts
contributed to 17.5%. In addition, the Hirshfeld surface of
[
[
2] (a) A. Kumar, M. Yang, M. Kim, F. P. Gabbaï, M. H. Lee, Organometallics
2017, 36, 4901; (b) A. Chowdhury, P. Howlader, P. S. Mukherjee,
Chem. A Eur. J. 2016, 22, 7468; (c) J. L. Fillaut, H. Akdas‐Kilig, E. Dean,
C. Latouche, A. Boucekkine, Inorg. Chem. 2013, 52, 4890; (d) A.
Dorazco‐Gonzalez, Organometallics 2014, 33, 868; (e) C. Y.‐S. Chung,
V. W.‐W. Yam, Chem. A Eur. J. 2014, 20, 13016.
2 3
Bi(PhBMes ) mapped with dnorm property is shown in Figure S10, in
which the dnorm surfaces highlighted in red represent contacts shorter
than the sum of the van der Waals radii of the two atoms; white
surfaces represent contacts close to the van der Waals radii and blue
3] (a) J. Lee, H.‐F. Chen, T. Batagoda, C. Coburn, P. I. Djurovich, M. E.
Thompson, Nat. Mater. 2016, 15, 92; (b) P.‐N. Lai, C. H. Brysacz, M.
K. Alam, N. A. Ayoub, T. G. Gray, J. Bao, T. S. Teets, J. Am. Chem.
Soc. 2018, 140, 10198; (c) C. Fan, C. Yang, Chem. Soc. Rev. 2014, 43,
[31]
surfaces represent longer contact distances.
6
439; (d) P. T. Chou, Y. Chi, Chem. A Eur. J. 2007, 13, 380.
4] M. A. Baldo, D. F. O'Brien, M. E. Thompson, S. R. Forrest, Phys. Rev. B
999, 60, 14422.
[
1
4
|
CONCLUSIONS
[
5] (a) L. Ji, S. Griesbeck, T. B. Marder, Chem. Sci. 2017, 8, 846; (b) L. Ji, R.
M. Edkins, L. J. Sewell, A. Beeby, A. S. Batsanov, K. Fucke, M. Drafz, J.
A. K. Howard, O. Moutounet, F. Ibersiene, A. Boucekkine, E. Furet, Z.
Liu, J. ‐F. Halet, C. Katan, T. B. Marder, Chem. A Eur. J. 2014, 20,
A novel bismuthine bearing three dimesitylborane moieties was pre-
pared, and adopted a distorted trigonal pyramidal structure in the solid
state. The X‐ray crystal structure analysis revealed short intermolecu-
lar C–H···H–C and C–H···C–C interactions, which were confirmed via
1
3618; (c) J. Li, C. Yang, X. Peng, Y. Chen, Q. Qi, X. Luo, W.‐Y. Lai,
W. Huang, J. Mater. Chem. C 2018, 6, 19; (d) S. Romero‐Servin, M.
Villa, R. Carriles, G. Ramos‐Ortiz, J.‐L. Maldonado, M. Rodriguez, M.
Guizado‐Rodriguez, Materials 2015, 8, 4258; (e) C. D. Entwistle, C.
D, T. B. Marder, Angew. Chem. Int. Ed. 2002, 41, 2927; (f) Z. M. Hud-
son, S. Wang, Acc. Chem. Res. 2009, 42, 1584; (g) A. Ito, K. Kawanishi,
E. Sakuda, N. Kitamura, Chem. A Eur. J. 2014, 20, 3940.
2 3
Hirshfeld surface analysis. The new Bi(PhBMes ) complex absorbed
light in the UV region and displayed a green fluorescence at room tem-
perature (RT) and a greenish‐blue phosphorescence at 77 K. DFT and
TD‐DFT calculations showed that the main three bands in the UV–vis
spectrum are LLCT that originated from mesityl/phenyl π orbitals to
boron empty p orbital/phenyl π* orbitals. A MLCT transition originat-
[
6] (a) C. R. Wade, A. E. J. Broomsgrove, S. Aldridge, F. P. Gabbaï, Chem.
Rev. 2010, 110, 3958; (b) F. Jakle, Chem. Rev. 2010, 110, 3985; (c) P.
C. A. Swamy, S. Mukherjee, P. Thilagar, Anal. Chem. 2014, 86, 3616;
2
ing from the Bi(III) 6s lone pair (HOMO‐18) to the empty p orbital on
(
d) J. K. Day, C. Bresner, N. D. Coombs, I. A. Fallis, L.‐L. Ooi, S. Aldridge,
boron (LUMO/LUOM+1) corresponded to the shoulder peak
appearing at λmax = 262 nm. NBO population analysis revealed
a +1.22 natural charge on the Bi(III) atom and a natural electronic con-
figuration of [core] 6s (1.73) 6p (2.04), which indicated a Lewis acidic
characteristic via using the empty 6p orbitals. Conversely, the second
Inorg. Chem. 2008, 47, 793; (e) A. E. J. Broomsgrove, D. A. Addy, C.
Bresner, I. A. Fallis, A. L. Thompson, S. Aldridge, Chem. A Eur. J. 2008,
14, 7525; (f) S. K. Mellerup, Y.‐L. Rao, H. Amarne, S. Wang, Org. Lett.
2016, 18, 4436; (g) Z. M. Hudson, X. Y. Liu, S. Wang, Org. Lett. 2011,
13, 300; (h) J. Feng, L. Xiong, S. Wang, S. Li, Y. Li, G. Yang, Adv. Funct.
Mater. 2013, 23, 340; (i) G. R. Kumar, S. K. Sarkar, P. Thilagar, Phys.

AMARNE ET AL.
7
Chem. Chem. Phys. 2015, 17, 30424; (j) S. Yamaguchi, S. Akiyama, K.
[15] C. R. Wade, M. R. Saber, F. P. Gabbaï, Heteroat. Chem. 2011, 22, 500.
Tamao, J. Am. Chem. Soc. 2001, 123, 11372.
[
16] (a) K. Behm, J. B. Essner, C. L. Barnes, G. A. Baker, J. R. Walensky, Dal-
ton Trans. 2017, 46, 10867; (b) K. Lyczko, J. Mol. Struct. 2017, 1127,
549; (c) D.‐W. Zhang, W.‐T. Chen, Y.‐F. Wang, Luminescence 2017,
32(2), 201; (d) Y. Kang, D. Song, H. Schmider, S. Wang, Organometal-
lics 2002, 21, 2413; (e) J. Ohshita, S. Matsui, R. Yamamoto, T.
Mizumo, Y. Ooyama, Y. Harima, T. Murafuji, K. Tao, Y. Kuramochi, T.
Kaikoh, H. Higashimura, Organometallics 2010, 29, 3239; (f) P. J.
Han, A. L. Rheingold, W. C. Trogler, Inorg. Chem. 2013, 52, 12033;
(g) E. J. Lee, J. S. Hong, T.‐J. Kim, Y. Kang, E. M. Han, J. J. Lee, K. Song,
D.‐U. Kim, Bull. Korean Chem. Soc. 2005, 26, 1946; (h) R. C. Smith, M.
J. Earl, J. D. Protasiewicz, Inorg. Chim. Acta 2004, 357, 4139; (i) R. C.
Evans, P. Douglas, C. Winscom, J. Coord. Chem. Rev. 2006, 250, 2093.
[
7] (a) N. Wang, M. Hu, S. K. Mellerup, X. Wang, F. Sauriol, T. Peng, S.
Wang, Inorg. Chem. 2017, 56, 12783; (b) G. R. Kumar, P. Thilagar, Inorg.
Chem. 2016, 55, 12220; (c) B. A. Blight, S. B. Ko, J. S. Lu, L. F. Smith, S.
Wang, Dalton Trans. 2013, 42, 10089; (d) Z. M. Hudson, C. Sun, M. G.
Helander, H. Amarne, Z. H. Lu, S. Wang, Adv. Funct. Mater. 2010, 20,
3426; (e) Z. M. Hudson, S. B. Zhao, R. Y. Wang, S. Wang, Chem. A Eur.
J. 2009, 15, 6131; (f) Y. L. Rao, D. Schoenmakers, Y. L. Chang, J. S. Lu,
Z. H. Lu, Y. Kang, S. Wang, Chem. A Eur. J. 2012, 18, 11306; (g) X.
Wang, Y. L. Chang, J. S. Lu, T. Zhang, Z. H. Lu, S. Wang, Adv. Funct.
Mater. 2014, 24, 1911; (h) Y. L. Rao, S. Wang, Inorg. Chem. 2009, 48,
7
698; (i) Z. M. Hudson, M. G. Helander, Z.‐H. Lu, S. Wang, Chem.
Commun. 2011, 47, 755; (j) Z. M. Hudson, S. Wang, Organometallics
011, 30, 4695; (k) S.‐B. Ko, J.‐S. Lu, Y. Kang, S. Wang, Organometal-
[
17] A. Gagnon, J. Dansereau, A. Le Roch, Synthesis 2017, 49, 1707.
18] P. Pyykko, Chem. Rev. 1988, 88, 563.
2
[
lics 2013, 32, 599; (l) Z. M. Hudson, C. Sun, M. G. Helander, Y.‐L.
Chang, Z.‐H. Lu, S. Wang, J. Am. Chem. Soc. 2012, 134, 13930; (m)
E. Sakuda, A. Funahashi, N. Kitamura, Inorg. Chem. 2006, 45, 10670.
[19] (a) C. G. Briand, N. Burford, Chem. Rev. 1999, 99, 2601; (b) R. Ge, H.
Sun, Acc. Chem. Res. 2007, 40, 267; (c) N. Yang, H. Sun, Coord. Chem.
Rev. 2007, 251, 2354; (d) P. J. Sadler, H. Li, H. Sun, Coord. Chem. Rev.
[
8] (a) Y. You, S. Y. Park, Adv. Mater. 2008, 20, 3820; (b) Q. Zhao, F. Li, S.
Liu, M. Yu, Z. Liu, T. Yi, C. Huang, Inorg. Chem. 2008, 47, 9256; (c) W.
Xu, S. Liu, H. Sun, X. Zhao, Q. Zhao, S. Sun, S. Cheng, T. Ma, L. Zhou,
W. Huang, J. Mater. Chem. 2011, 21, 7572; (d) S. Sharma, H. Kim, Y.
H. Lee, T. Kim, Y. S. Lee, M. H. Lee, Inorg. Chem. 2014, 53, 8672; (e)
G. Zhou, C.‐L. Ho, W. Y. Wong, Q. Wang, D. Ma, L. Wang, Z. Lin, T.
B. Marder, A. Beeby, Adv. Funct. Mater. 2008, 18, 499; (f) W.‐J. Xu,
S.‐J. Liu, X.‐Y. Zhao, S. Sun, S. Cheng, T.‐C. Ma, H.‐B. Sun, Q. Zhao,
W. Huang, Chem. A Eur. J. 2010, 16, 7125; (g) R. S. Vadavi, H. Kim, K.
M. Lee, T. Kim, J. Lee, Y. S. Lee, M. H. Lee, Organometallics 2012, 31,
1
999, 185‐186, 689; (e) J. C. Berrones‐Reyesa, C. C. Vidyasagara, B.
M. M. Floresa, V. M. Jiménez‐Péreza, JOL 2018, 195, 290; (f) H. Li,
H. Sun, Curr. Opin. Chem. Biol. 2012, 16, 74; (g) D. M. Keogan, D. M.
Griffith, Molecules 2014, 19, 15258; (h) A. Pathak, V. L. Blair, R. L.
Ferrero, M. Mehring, P. C. Andrews, Chem. Commun. 2014, 50,
1
5232; (i) H. Xu, S. Abdulghani, J. Behiri, A. Sabokbar, J. Biomed.
Mater. Res. B Appl. Biomater. 2005, 75, 64; (j) Y. Delaviz, Z.‐X. Zhang,
I. Cabasso, J. Smid, J. Appl. Polym. Sci. 1990, 40, 835; (k) E. R. T.
Tiekink, Critical Rev. Oncol./Hematol. 2002, 42, 217; (l) A. Raheel, D.
Imtiaz‐ud‐Din, S. Andleeb, S. Ramadan, M. N. Tahir, Appl. Organomet.
Chem. 2017, 31(6), e3632.
31; (h) X. Yang, Z. Huang, C.‐L. Ho, G. Zhou, D. R. Whang, C. Yao, X.
Xu, S. Y. Park, C.‐H. Chui, W.‐Y. Wong, RSC Adv. 2013, 3, 6553; (i) T.
Kim, S. Lim, S.‐R. Park, C. J. Han, M. H. Lee, Polymer 2015, 66, 67; (j)
A. Ito, T. Hiokawa, E. Sakuda, N. Kitamura, Chem. Lett. 2011, 40, 34.
[
[
20] W.‐L. Jia, D.‐R. Bai, T. McCormick, Q.‐D. Liu, M. Motala, R.‐Y. Wang,
C. Seward, Y. Tao, S. Wang, Chem. A Eur. J. 2004, 10, 994.
21] Gaussian 09, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.
A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F.
Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara,
K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, T. Vreven, J. Montgomery, J. E. Peralta, F. Ogliaro,
M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R.
Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S.
Iyengar, J. Tomasi, M. Cossi, N. Rega, N. J. Millam, M. Klene, J. E.
Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.
E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth,
P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas,
J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox
[9] (a) A. Nakagawa, A. Ito, E. Sakuda, S. Fujii, N. Kitamura, Inorg. Chem.
2018, 57, 9055; (b) A. Nakagawa, A. Ito, E. Sakuda, S. Fujii, N.
Kitamura, Eur. J. Inorg. Chem. 2017, 2017, 3794; (c) A. Nakagawa, E.
Sakuda, A. Ito, N. Kitamura, Inorg. Chem. 2015, 54, 10287; (d) Y.
Sun, Z. M. Hudson, Y. L. Rao, S. Wang, Inorg. Chem. 2011, 50, 3373;
(
e) E. Sakuda, Y. Ando, A. Ito, N. Kitamura, Inorg. Chem. 2011, 50,
603; (f) C. R. Wade, F. P. Gabbaï, Inorg. Chem. 2010, 49, 714.
1
[
10] (a) Y. Kang, A. Ito, E. Sakuda, N. Kitamura, Bull. Chem. Soc. Jpn. 2017,
90, 574; (b) Y. Kang, A. Ito, E. Sakuda, N. Kitamura, J. Photochem.
Photobiol., A: Chemistry 2015, 313, 107; (c) A. Ito, Y. Kang, S. Saito,
E. Sakuda, N. Kitamura, Inorg. Chem. 2012, 51, 7722; (d) S.‐T. Lam,
N. Zhu, V. W.‐W. Yam, Inorg. Chem. 2009, 48, 9664.
[
[
[
11] (a) Y. Sun, N. Ross, S.‐B. Zhao, K. Huszarik, W.‐L. Jia, R.‐Y. Wang, D.
Macartney, S. Wang, J. Am. Chem. Soc. 2007, 129, 7510; (b) S.‐B.
Zhao, T. McCormick, S. Wang, Inorg. Chem. 2007, 46, 10965.
[
[
[
[
22] N. M. O'Boyle, A. L. Tenderholt, K. M. Langner, J. Comput. Chem.
2
008, 29, 839.
12] (a) P. C. A. Swamy, P. Thilagar, Dalton Trans. 2016, 45, 4688; (b) Y. H.
Lee, N. V. Nghia, M. J. Go, J. Lee, S. U. Lee, M. H. Lee, Organometallics
23] E. D. Glendening, A. E. Reed, J. E. Carpenter, F. Weinhold. NBO
Version 3.1, TCI, University of Wisconsin, Madison 1998.
2014, 33, 753.
24] G. M. Sheldrick, SHELXL97, Program for Crystal Structure Refinement,
University of Göttingen, Göttingen, Germany 1997.
13] (a) C. L. Dorsey, P. Jewula, T. W. Hudnall, J. D. Hoefelmeyer, T. J. Tay-
lor, N. R. Honesty, C.‐W. Chiu, M. Schulte, F. P. Gabbaï, Dalton Trans.
25] S. K. Wolff, D. J. Grimwood, J. J. McKinnon, M. J. Turner, D.
Jayatilaka, M. A. Spackman, CrystalExplorer 3.1, University of Western
Australia, Crawley, Australia 2012.
2008, (33), 4442; (b) M. H. Lee, F. P. Gabbaï, Inorg. Chem. 2007, 46,
8132; (c) M. Melaimi, F. P. Gabbaï, J. Am. Chem. Soc. 2005, 127,
9680; (d) M. Melaimi, F. P. Gabbaï, Z. Anorg. Allg. Chem. 2012, 638,
1; (e) T. W. Hudnall, C.‐W. Chiu, F. P. Gabbaï, Acc. Chem. Res. 2009,
42, 388.
[
[
26] R. J. F. Berger, D. Rettenwander, S. Spirk, C. Wolf, M. Patzschke, M.
Ertl, U. Monkowius, N. W. Mitzel, Phys. Chem. Chem. Phys. 2012, 14,
1
5520.
27] (a) C. Silvestru, H. J. Breunig, H. Althaus, Chem. Rev. 1999, 99, 3277;
b) M. Hébert, P. Petiot, E. Benoit, J. Dansereau, T. Ahmad, A. Le Roch,
X. Ottenwaelder, A. Gagnon, J. Org. Chem. 2016, 81, 5401.
[28] L. Shimoni‐Livny, J. P. Glusker, C. W. Bock, Inorg. Chem. 1998, 37, 1853.
[
14] (a) H. Zhao, F. P. Gabbaï, Nat. Chem. 2010, 2, 984; (b) C. R. Wade, F. P.
Gabbaï, F. Z. Naturforsch 2014, 69b, 1199; (c) H. Zhao, L. A. Leamer, F.
P. Gabbaï, Dalton Trans. 2013, 42, 8164; (d) C. R. Wade, F. P. Gabbaï,
Organometallics 2011, 30, 4479; (e) M. Schulte, F. P. Gabbaï, Chem.
A Eur. J. 2002, 8, 3802.
(

8
AMARNE ET AL.
[
[
29] S. Alvarez, Dalton Trans. 2013, 42, 8617.
30] S. Rosel, H. Quanz, C. Logemann, J. Becker, E. Mossou, L. Canadillas‐
Delgado, E. Caldeweyher, S. Grimme, P. R. Schreiner, J. Am. Chem. Soc.
How to cite this article: Amarne H, Helal W, Wang S. Synthe-
sis, structure and density functional theory calculations of a
novel photoluminescent trisarylborane–bismuth(III) complex.
Luminescence. 2019;1–8. https://doi.org/10.1002/bio.3667
2
017, 139, 7428.
31] J. J. McKinnon, D. Jayatilaka, M. A. Spackman, Chem. Commun. 2007,
814.
[
3
SUPPORTING INFORMATION
Additional supporting information may be found online in the
Supporting Information section at the end of the article.