Achieving yellow emission by varying the donor/acceptor units in rod-shaped fluorenyl-alkynyl based π-conjugated oligomers and their binuclear gold(i) alkynyl complexes

Article abstract of DOI:10.1039/c7dt00895c

Fluorenyl-alkynyl based π-conjugated rod-shaped oligomers bearing different central aromatic moieties and functionalizable di-alkynyl termini, such as H - Fl - Fl - Fl - H (OH1), H - Fl - Btz - Fl - H (OH2) and H - Fl - Btd - Fl - H (OH3) where Fl = 9,9-d

Full text of DOI:10.1039/c7dt00895c

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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a Zr-metal–organic
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Achieving Yellow Emission by Varying Donor/Acceptor Units in
Rod-shaped Fluorenyl-alkynyl Based π-Conjugated Oligomers and
Their Binuclear Gold(I) Alkynyl Complexes
Received 00th January 20xx,
Accepted 00th January 20xx
Sk Najmul Islam,a Amit Sil,a and Sanjib K. Patra*a
DOI: 10.1039/x0xx00000x
Fluorenyl-alkynyl based π-conjugated rod-shaped oligomers bearing different cetntral aromatic moieties and
functionalizable di-alkynyl termini, such as H−≡−Fl−≡−Fl−≡−Fl−≡−H (OH1), H−≡−Fl−≡−Btz−≡−Fl−≡−H (OH2) and
H−≡−Fl−≡−Btd−≡−Fl−≡−H (OH3) where Fl = 9,9-dioctylfluorene, Btz = N-hexylbenzotriazole, Btd = benzothiadiazole, were
successfully synthesized by Pd(0) catalyzed Stille coupling protocol. Electron withdrawing benzothiadiazole and
benzotriazole as strong to moderate acceptor, and fluorene as donor have been incorporated to adjust the Donor-
Acceptor (D-A) strength for fine tuning of the bandgap (Eg) as well as the emission wavelength. The corresponding digold(I)
σ-complexes, (PPh3)Au−≡−Fl−≡−Fl−≡−Fl−≡−Au(PPh3) (OM1), (PPh3)Au−≡−Fl−≡−Btz−≡−Fl−≡−Au(PPh3) (OM2) and
(PPh3)Au−≡−Fl−≡−Btd−≡−Fl−≡−Au(PPh3) (OM3) have also been prepared by reaction of Au(PPh3)Cl and methanolic NaOMe
in DCM with the corresponding alkynyl functionalized oligomers, to take the advantage of heavy-atom effect on their
emissive properties. The synthesized rod-shaped π-conjugated fluorene based oligomers and their binuclear Au(I) σ-
complexes have been unambiguously characterized by various spectroscopic tools such as FTIR, multinuclear NMR as well
as MALDI-TOF and CHN analyses. The absorption and emission spectral studies exhibited a progressive red shift with
increasing electron withdrawing character of the central aromatic unit. The rod-like oligomers having alkynyl termini and
the corresponding digold(I) complexes are found to be blue, cyan and yellow emissive, demonstrating fine tuning of the
emission wavelength. Most importantly, the fluorene based π-conjugated yellow light emitter OH3 and OM3 are
successfully achieved by varying donor/acceptor moiety to the fluorenyl-alkynyl backbone. The digold(I) diacetylide
organometallic wires exhibit phosphorescence at 77 K in degassed CH2Cl2 due to the efficient intersystem crossing from
www.rsc.org/
the
S1
to
the
T1
excited
state
as
induced
by
heavy
atom.
yellow in combination with sky blue emission is also one of the
key components for the construction of white OLEDs.6 Handful
yellow light emitting materials based on semiconducting
carbon dots, quantum dots, π-conjugated organic and
organometallic compounds are reported till date. Carbon dots
mostly show strong emission only in the blue region exhibiting
weak emission in the long-wavelength (yellow to red light),
which restricts their further application.7 Quantum dots based
light emitting materials mostly contain cadmium or lead which
have negative environmental and ecological impacts for its
high toxicity. Consequently, it hinders their commercial
application as light emitting diodes.8 Therefore, development
of highly efficient π-conjugated yellow emissive organic and
organometallic congeners is essential and in high demand.
Singlet-triplet intersystem crossing induced by the third row
transition and late transition elements in conjunction with the
π-conjugated ligands is an attractive strategy for tuning
desired emission wavelength. In this regard, yellow iridium(III)
cyclometalled complexes are found to be exciting materials for
full-colour display and white OLEDs.1c,5a,6a,9 Pt(II) metal
complexes were explored by various groups as a promising
candidate for yellow emissive materials.10 Phosphorescent
Re(I)-polypyridine complexes have been reported as a intense
Introduction
There is a rapidly growing interest in designing and developing
of rigid-rod metal-acetylide organometallic oligomers and
polymers (metallopolyynes) for smart applications in
optoelectronics such as in flexible organic photovoltaics (OPV),
organic light emitting diodes (OLED), and field effect
transistors (FET).1 In this regard, a considerable amount of
interest has been focused on developing organic light-emitting
materials for OLED application.2 Many blue, green and red light
emitting organic and organometallic conjugates have been
developed,3 but highly efficient and stable yellow light
emitting organic and organometallic materials are still rare.4
The yellow emitting materials are used as a lighting source for
lithography, signal lights and full-colour display.5 In addition,
aDepartment of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur-
721302, WB, India, E-mail: skpatra@chem.iitkgp.ernet.in. Tel: +913222283338
†Electronic Supplementary Information (ESI) available: Syntheses and
characterization of fluorenyl-alkynyl oligomers, additional photophysical studies,
electrochemical and thermal characterization, crystallographic data for O3 (CCDC
1512387). See DOI: 10.1039/x0xx00000x
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and long lived yellow emissive materials.11 Highly luminescent moieties through stepwise synthetic protocol. Electron
Ln(III) complexes have also been utilized as a yellow light withdrawing benzothiadiazole and benzotriazole as strong to
emitting materials.12 Extended π-conjugated congeners moderate acceptor, and fluorene as a weak donor have been
derived from naphthalene diimide13 and organoboron14 based incorporated to adjust the D-A strength to tune the bandgap
derivatives have been found to be promising yellow light (Eg) and hence the emission wavelength. The alkynyls termini
emiting materials as reported. Alkyl substituted soluble in the rod-like oligomers offer the opportunity to introduce
fluorene based π-conjugated oligomers and polymers have Au(I) fragments to achieve phosphorescent organometallic
emerged as a very promising candidate for OLED applications molecular wires with the consequence of triplet state
due to their high photoluminescent quantum yield, good emission.
chemical and thermal stability, excellent solubility, good film-
forming property and possibility of energy level alignment by
Results and discussion
engineering the band gap through chemical functionalization.
However, fluorene based oligomers and polymers exhibit
emission in the blue region, allowing for using only as blue-
light emitter.15 Recently, fluorene based oligomers and
polymers have attracted potential interest as yellow light
emitting materials4a,16 which are achieved by adjusting the
bandgap through incorporation of electron deficient moiety to
the fluorene backbone.17 Several electron deficient monomers
have been reported as the co-monomers to be incorporated
into the backbone of wide bandgap oligomers and polymers.
Among them, 2,1,3-benzothiadiazole (Btd) and its derivatives
have great importance as building blocks for promising organic
semiconducting materials due to their higher electron
deficiency. For example, Jen and coworkers have
demonstrated efficient green emitting copolymers of 9,9-
dioctylfluorene (Fl) and Btd,18 whereas a series of red emitting
copolymers based on Fl and 4,7-di-2-thienyl-2,1,3-
benzothiadiazole have been reported by Cao and coworkers.19
The recent development of π-conjugated rigid-rod metal-
acetylide organometallic wires has attracted great interest as
smart materials for its emerging optoelectronic application.20
Efficiency of organic light emitting diodes is typically controlled
by the presence of triplet state emission, which can be
achieved by the incorporation of heavy metals to the π-
conjugated organic backbone. The strong spin-orbit coupling,
induced by the heavy metals, mixes the singlet and triplet
excited states through efficient intersystem crossing (ISC),
which allows to measure the spin-forbidden triplet emission
(phosphorescence) experimentally. In this regard, the
photophysical properties of gold(I/III)─σ-acetylide complexes
have received much current attention due to their rich
photophysical properties.21 The presence of gold(I) with
tertiary phosphine ligands constituting a linear geometry
through σ-alkynyl unit of the π-conjugated alkynyl termini,
makes it most attractive and promising candidate for the
construction of linear organometallic molecular wires, which
may possess unique properties such as long-lived
phosphorescence,22 liquid-crystallinity,23 and nonlinear optical
behaviour24 allowing its applications in electronic devices.25
Furthermore, Au(I)···Au(I) interaction plays an important role
resulting strong luminescence properties in many Au(I)
complexes of wide range of molecular structures.26
Synthesis and characterization
A stepwise synthetic protocol has been followed to develop
yellow light emitting fluorene based emitter. A series of
fluorene based π-conjugated D-π-A-π-D rod-shaped oligomers
were synthesized by varying the π-conjugated organic spacers
in between two fluorenyl-alkynyl units, following Stille
coupling protocol as shown in Scheme 1. Incorporation of alkyl
group is necessary to improve the solubility and solution
processability of the fluorene based rigid oligomers. Hence 2-
bromo-7-((trimethylsilyl)ethynyl)-9,9-dioctylfluorene (4) was
selected as a key starting material for the alkynyl appended
precursor, which was synthesized by adaptation of the
literature procedure starting from fluorene.27 The desired rod-
like π-conjugated fluorene based trimer with alkynyl termini
(O1) was obtained by Stille coupling between 4 and the
stanylated derivative (
treating LDA and tributylstannylchloride on diethynyl-
functionalized fluorene ( ). To tune the emission to a longer
9) which was generated in-situ by
8
wavelength, electron withdrawing benzotriazole (Btz) group
was intended to incorporate in between the two fluorene
moieties connected through ─C≡C─ units. Thus the rod-like π-
conjugated fluorene-benzotriazole based D-π-A-π-D oligomer
(
O2) conjugated with alkynyl spacers was synthesized by Stille
coupling between 15 and 4. After successful inclusion of
benzotriazole in fluorene moieties, stronger acceptor unit such
as benzothiadiazole (Btd) was also incorporated to the
fluorenyl-alkynyl backbone to further modulate its
photophysical properties, specially the emission wavelength.
Therefore Pd(0)-catalyzed Stille coupling between 4 and 20
was accomplished to afford the desired rod-like π-conjugated
benzothiadiazole-fluorene hybrid with alkynyl termini and
spacers (O3) exhibiting yellow emission as desired. Column
chromatography (silica gel) using EtOAc/hexanes as eluent
afforded analytically pure O1-O3 in 61-64% yield, which were
characterized by 1H, 13C and DEPT-135 NMR studies confirming
its chemical structures.† Formation of the oligomers were
further confirmed by MALDI-TOF study, exhibiting the
molecular ion peaks at 1407.088, 1219.905 and 1152.766
([M+H]+) respectively. After several attempts by varying
crystallization techniques and conditions, the orange needle-
like single crystals suitable for X-ray crystallography were
successfully harvested by layering MeOH on DCM
With these ideas in mind, we aim to develop yellow light
emitting D-π-A-π-D type of fluorenyl-alkynyl based oligomers
with alkynyl spacers and termini by varying donor/acceptor
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Scheme 1 Synthesis of the binuclear gold(I) σ-complexes
Reagents and conditions: a) 3 mol% Pd(PPhh3)4, THF, reflux, 24 h; b) K2CO3, DCM, MeOH, 28 oC, 4 h; c) 2.1 eqv. of
Au(PPh3)Cl, NaOMe, MeOH, DCM, 28 oC, 12 h.
(
OM1 and OM2) and 42.9 ppm (OM3) attributed to the Au(I)-
solution of O3. It crystallized in P-1 space group having two coordinated PPh3, suggests the formation of digold(I)
independent molecules in the asymmetric unit. Disorder and diacetylide organometallic wires having symmetrical -C≡C-
higher thermal vibration which are very common for the long Au(PPh3) terminal groups in solution (Fig. S25, S41 and S56†).
chain octyl and terminal trimethylsilyl groups respectively The organometallic wires were further characterized by
resulted relatively higher R1 and wR2 values calculated from multinuclear NMR and IR spectra, mass spectrometry as well
data with I>2
polyyne, O3 has been confirmed unambiguously from the spectra with the integration value of selected proton signals of
single crystal X-ray structural determination as depicted in Fig. OM1 OM3 is depicted in Fig. 1. The multiplicity of the proton
S108†.
σ
(I).28 However, the rigid rod skeleton of the as by elemental analysis. The comparison of the 1H NMR
-
signals and the associated relative intensities unambiguously
confirm the proposed structures. In 13C{1H} NMR the
Synthesis of Binuclear Au(I) Alkynyl σ-Complexes. After characteristic signal at 105.4 ppm (for OM1 and OM2) and at
successful synthesis of blue, cyan and yellow luminescent 105.5 ppm (OM3) indicate the presence of carbon attached to
fluorenyl-alkynyl based π-conjugated rod-like oligomers, Au(I) gold(I) (Au-C≡C), which are further confirmed by the
was incorporated into the π-conjugated organic backbone to disappearance of the resonance at 105.4 ppm (for OM1 and
take the advantage of heavy atom effect in their OM2) and at 105.5 ppm (OM3) in DEPT-135 NMR.21n,29 The
photophysical properties, aiming for spin forbidden triplet characteristic ῡC≡C (C≡C aꢀached to Au(I)) stretching frequency
yellow emission (phosphorescence) induced by strong spin- for all the organometallic complexes (OM1
orbit coupling. One of the elegant strategies to construct linear 2200-2204 cm-1 which are subsequently higher than their
main-chain metallopolyyne with extensive electronic parent analogues (OH1
OH3) by ca. 100 cm-1.30 Finally, the
conjugation is through the formation of linear two-coordinate organometallic wires OM1 OM3 were characterized by
gold(I)─acetylide (Au─C≡C-) bond. All the π-conjugated MALDI-TOF, revealing the molecular ion peaks, ([M+H]+) at
oligomers O1 O2 and O3 having trimethylsilylalkynyl termini 2180.158, 1992.790 and 1925.690 respectively. The isotopic
-OM3) appears at
-
(
-
)
,
at the both ends were desilylated by a base-promoted distribution pattern for the molecular ion peak obtained from
deprotection using K2CO3 as base in DCM/MeOH to obtain the experimental data is in perfect agreement with the
OH1
,
OH2 and OH3 respectively with alkynyl (-C≡C-H) termini. simulated data for all the digold(I) diacetylide complexes as
OM2 shown in Fig. 2.
The corresponding digold(I) diacetylide complexes (OM1
,
and OM3) were synthesized by treating with 2.1 eqv. of
Au(PPh3)Cl in presence of NaOMe in MeOH as outlined in
Scheme 1. The binuclear Au(I) σ-complexes were purified by
precipitating their concentrated CH2Cl2 solution in anhydrous
MeOH, followed by a short column chromatography (neutral
alumina) using dry EtOAc/hexanes (1:20) as eluent in inert
atmosphere to achieve analytically pure organometallic
molecular wires OM1-OM3 in 88-92% yield respectively.
31P{1H} NMR spectra of the analytically pure Au(I)
organometallic complexes, exhibiting singlet resonance at 42.7
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reduction process becomes quasi-reversible for the
corresponding Au(I) complex, OM3. As there is no prominent
reduction process for OH1-OH2 and OM1-OM2, we have
calculated the ELUMO levels from the values of EHOMO and its
optical band gaps (ELUMO = EHOMO + Egopt).6d,15g,17a The ELUMO
energy levels of OH1-OH3 are calculated as -3.05, -3.17, and -
3.53 eV. The ELUMO energy levels of OM1- OM3 are -3.04, -3.18,
and -3.57 eV. Incorporation of electron withdrawing aromatic
units into the π-conjugated backbone lowers down the ELUMO
energy, which is reflected in the energy levels of OH1 to OH3
consequently OM1 to OM3.
,
Table
1 Electrochemical data and HOMO-LUMO
energy levels.
Compound
Eoxonset, V
EHOMO, eVa
ELUMO, eVb
OH1
OH2
OH3
OM1
OM2
OM3
1.16
1.14
1.19
1.09
1.08
1.17
-5.87
-5.85
-5.90
-5.80
-5.79
-3.05
-3.17
-3.53
-3.04
-3.18
-3.57
Fig. 1 1H NMR (600 MHz, CDCl3) spectra with the integral
ratio of the protons in OM1-OM3
.
-5.88
b
aEHOMO (eV) = -(Eoxonset + 4.71). (ELUMO = EHOMO + Egopt).
Egopt values are estimated from solid state absorption
spectra (vide infra).
Thermal analysis. Thermal properties of these fluorenyl-
alkynyl based π-conjugated oligomers and the Au(I) complexes
were examined by thermogravimetric analyses (TGA) and
differential scanning calorimetry (DSC). TGA study clearly
indicates that all the fluorene based π-conjugated oligomers
and their Au(I) complexes have good thermal stability. The
decomposition temperatures for OH1 to OH3 are found to be
380, 151 and 154 oC respectively with ca. 2% weight loss as
observed for the similar rod-shaped oligomers.22h The
Fig. 2 Experimental and simulated isotopic distribution
pattern for the molecular ion peaks ([M+H]+) of OM1-
OM3 respectively, obtained from MALDI-TOF MS.
decomposition temperatures for OM1-OM3 were observed at
o
208, 191 and 187 C respectively. In case of the π-conjugated
oligomers, weight loss of 44-48% was observed at 486, 508
and 498 oC due to removal of alkyl groups, whereas for the
digold(I) diacetylide complexes, the weight loss of 24-50% can
be ascribed to the removal of PPh3 and alkyl groups at 454,
459 and 455 oC. While recording DSC, the glass-transition
temperatures (Tg) for O1 to O3 with trimethylsilylalkynyl
termini were observed at 57, 49 and 47 oC. For the
Electrochemical properties. To understand the influence of the
acceptor properties of Btz and Btd units on the HOMO-LUMO
energy levels, the cyclic voltammetric experiments of the rigid
rod-like π-conjugated oligomers and their corresponding
digold(I) diacetylide complexes were conducted (Fig. S92†). For
this purpose, film of the synthesized π-conjugated oligomers
and their binuclear Au(I) complexes were prepared by drop
casting the corresponding DCM solution on GC-disc electrode.
The measurement was carried out in CH3CN using n-Bu4NPF6
(0.1 M) as supporting electrolytes, Pt wire counter electrode
and Ag/AgCl reference electrode. The electrochemical data are
summarized in Table 1. HOMO energy levels were calculated
from the onset oxidation potentials considering EHOMO (eV) = -
(Eoxonset + 4.71).31 The EHOMO energy levels of OH1 to OH3 are
calculated as -5.87, -5.85, and -5.90 eV based on their onset
oxidation potential. Similarly the calculated EHOMO energy
levels of OM1 to OM3 are -5.80, -5.79, and -5.88 eV. OH3
corresponding digold(I) σ-complexes (OM1-OM3), Tgs were
determined as 46, 42 and 38 oC. With increasing the
substituents on π-conjugated backbone, the mobility of the
molecule decreases leading to increase in chain rigidity and
Tg.32 Hence, Tg decreases from OM1 to OM3 with decreasing
the numbers of alkyl substituents and consequent reduction in
rigidity in the molecular chain.
Absorption and photoluminescence studies. All the new π-
conjugated rod-shaped oligomers are air stable and highly
soluble in common organic solvents even in hexanes. The good
solubility of the π-conjugated oligomers and their
exhibits a reversible redox wave at E1/2 = -1.17(80) V
corresponding to the Btd acceptor unit. However, the
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corresponding rigid-rod organometallic wires allowed us to series of D-π-A-π-D based oligomer, as the acceptor property
explore the photophysical properties in solution. The of the former is relatively higher. The absorbance data of OH1
electronic absorption of the compounds OH1-OH3 and their to OH3 and their corresponding digold(I) σ-complexes are
corresponding digold(I) diacetylide complexes (OM1-OM3
)
tabulated in Table 2. The absorption spectra of O1-O3 were
was studied in distilled and degassed 1,2-DCE at 298 K. The also studied showing similar photophysical properties to the
absorption maxima (λmax) associated with the π-π* transition alkynyl substituted analogues (Fig. S82 and Table S1†).
of the π-conjugated oligomers OH1 and OH2 were 384 nm (ɛ=
9.25 × 104 M-1 cm-1) and 401 nm (ɛ= 5.57 × 104 M-1 cm-1)
whereas the absorption maxima for their corresponding Au(I)
organometallic wires were slightly red shifted by 7-9 nm (Fig.
3) with similar ɛ values. Interestingly, OH3 and OM3 show two
distinct absorption bands. The absorption band with shorter
wavelength at 332 nm (ɛ= 4.32 × 104 M-1 cm-1) and 350 nm (ɛ=
6.53 × 104 M-1 cm-1) for OH3 and OM3 respectively are
assigned as π-π* transition. The absorption bands of low
energy at 445 nm (ɛ= 2.60 × 104 M-1 cm-1) and 453 nm (ɛ= 3.32
Fig. 3 Normalized absorption spectra of OH1-OH3 and
OM1-OM3 recorded as (a) ~1x10-5 M solution in degassed
1,2-DCE (b) thin film (spin coated on quartz plate).
× 104 M-1 cm-1) are attributed to intramolecular charge transfer
(ICT) between electron-rich fluorene and electron-deficient
benzothiadiazole moiety.17a The solid state absorption spectra
for OH1
-OH3 and the digold(I) diacetylide complexes were
Highly emissive nature of all the compounds both in
recorded as thin films spin coated on quartz substrates. The solution and solid state prompted us to study the emission
maximum red shift in absorption maxima were observed for properties systematically to understand the structure-property
OH3 (8 nm) and OM3 (13 nm) in solid state. The insignificant relationship. The emission of the rod-shaped alkynyl
bathochromic shift in solid state absorption spectra for all the functionalized
fluorophores
(
OH1
-
OH3
)
and
their
oligomeric and organometallic wires suggests the rigid-rod corresponding digold(I) diacetylide complexes was studied in
structure having extensive π-conjugation even in solution degassed 1,2-DCE in the order of 10-5 M concentration at 298
ensured by acetynyl bridges in between the aromatic units. K. The emission data is tabulated in Table 3. The intense
The optical bandgap (Egopt) for OH1
-OH3 and OM1-OM3 are emission with λmax in the rage of 412-564 nm is assigned as
2.82, 2.68, 2.37, 2.76, 2.61, and 2.31 eV respectively as intraligand π-π* transition (i.e., S1 → S0).33 OH1 and OH2
calculated from the onset of solid state absorption by using exhibit structured emission with major emission centered at
the equation Egopt(eV) = 1240/λcut off. The bandgap of the 412 and 433 nm. Interestingly, OH3 having benzothiadiazolyl-
binuclear Au(I) σ-complexes are lower than their alkynyl moiety in between the fluorenyl-alkynyl units shows
corresponding oligomers, suggesting enhanced π-conjugation relatively broad emission centered at 542 nm, with
a
of the ligands through the metal orbitals. Most importantly, remarkable bathochromic shift compared to the other rigid-
the absorption studies suggest that the bandgap can be tuned rod π-conjugated oligomers. The similar emission behavior was
successfully by varying the electron withdrawing property of observed for the trimethylsilyl protected oligomers with
the π-conjugated aromatic spacers in between the two alkynyl termini, O1-O3 (Fig. S83 and Table S2†). The emission
fluorene moieties connected through acetynyl groups. Thus maxima for their corresponding digold(I) diacetylide complexes
bandgap decreases significantly in case of benzothiadiazole were red shifted
(OH3) than the benzotriazole (OH2) as the acceptor unit in this
Table 2 Absorbance data of OH1-OH3 and their Au(I) σ-complexes (OM1-OM3
)
Absorption
Solutiona
Thin flimb
λmax, cut off
439
Compound
λmax, nm (ɛ×104 M-1cm-1 )
294 (sh), 370 (sh), 384 (9.25)
302 (3.34), 329 (3.06), 401 (5.57), 426
(sh)
λmax, nm
Eg, eV (optical)
2.82
OH1
OH2
297, 371, 385
304, 331, 408, 434
463
2.68
OH3
OM1
OM2
332 (4.32), 344 (sh), 445 (2.60)
378 (sh), 391 (10.39)
327, 342, 453
396
523
449
473
2.37
2.76
2.61
315 (3.54), 342 (4.21), 360 (4.87), 410
(6.64), 435 (sh)
322, 346, 368, 421,
446 (sh)
OM3
350 (6.53), 453 (3.32)
357, 466
535
2.31
a ~1 × 10-5 M 1,2-DCE solution at 298 K. bMeasured as thin films on quartz substrates.
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Table 3 Emission data of OH1-OH3 and their Au(I) σ-complexes (OM1-OM3
)
Emission
Solutiona
Thin flimb
Compound
λem (λex), nm
412, 433 (384)
449, 474 (401)
542 (445)
Quantum Yield (Φ)
Stokes Shift, cm-1
1769
λem (λex), nm
472, 499 (385)
509 (408)
OH1
OH2
OH3
OM1
OM2
OM3
0.42
0.39
0.26
0.27
0.21
0.13
2665
4021
551 (453)
426, 443 (sh) (391)
462, 485 (410)
564 (453)
2101
474 , 504 (396)
519 (421)
2745
4344
566 (466)
a ~1 × 10-5 M in 1,2-DCE solution at 298 K. bMeasured as thin films on quartz substrates.
by 14-22 nm compared to that of the parent analogues with The bathochromic shift in the emission wavelength with
alkynyl termini. The photoluminescence spectra of OH1 OH3 increasing solvent polarity for OH3 and OM3 having
and the corresponding binuclear Au(I) σ-complexes (OM1 benzothiadiazole as acceptor unit suggests that the first
-
,
-
OM3) suggests that they are blue, cyan and yellow emitters excited state has higher dipole moment compared to its
respectively (Fig. 4). The modulation of the π-acceptor groups ground state.35
by increasing the strength of acceptor units in between two
fluorene moieties results in significant perturbation in the
photonic properties, demonstrating tuning of the PL
wavelength. Most importantly, the strategy to incorporate
benzothiadiazole in between the two fluorene units attached
through alkynyl spacers has successfully renders yellow
emission. Thus, the desired yellow emissive material was
successfully achieved by fine tuning of the acceptor unit in the
D-π-A-π-D molecular systems. These yellow emissive fluorenyl-
alkynyl based π-conjugated molecular wires are of interest for
potential application as yellow light emitters. The PL quantum
yields were calculated by using the absolutely measured
quantum yield of quinine sulphate in degassed 0.1 M H2SO4
solution as reference. Quantum yield decreases from 0.42 to
0.26 on moving from OH1 to OH3, suggesting strong donor-
acceptor interaction leading to quenching in fluorescence.34
Incorporation of heavy metal species, Au(I) further causes
decrease in quantum yield because of strong spin-orbit
coupling. No change in emission intensity of the
organometallic wires was observed while studying in oxygen
saturated solvent suggesting that the origin of the emission is
presumably due to singlet state. The absorption and the
Fig. 4 Normalized PL spectra of OH1-OH3 and OM1-OM3
recorded as (a) ~1x10-5 M solution in degassed 1,2-DCE
(b) thin film (spin coated on quartz plate).
Fig. 5 (a) Visual appearance of OM3 in different solvents
under UV illumination at 365 nm. (b) Normalized PL
spectra of OM3 in solvent with different polarity.
emission spectra of OH1-OH3 and OM1-OM3 were also
measured in different solvents to demonstrate the
dependence of photophysical properties on polarity of the
Solid state emissive organic chromophores are of
considerable interest for practical thin-film device applications,
such as organic light emitting diodes, organic solid state lasers,
organic field-effect transistors, nonlinear optics, organic
photovoltaics (OPV).36 In general, the luminescence of π-
conjugated oligomeric compounds is quenched in the solid
state due to the enhanced nonradiative deactivation via
intermolecular interaction.37 Interestingly, in our case an
appreciable amount of emission in the solid state was
medium. The absorption spectra of OH1
were not sensitive to the solvent polarity. The emission
spectra of OH1 OH2 and OM1 OM2 were also insensitive with
-OH3 and OM1-OM3
-
-
different solvent polarity. However, for OH3 and OM3, a
remarkable bathochromic shift in λem was observed with
increasing solvent polarity (Fig. 5 and S85†). The emission
maxima is shifted by 40 nm and 53 nm with increasing polarity
from hexanes (0.0) to acetone (5.1) for OH3 and OM3
respectively. Maximum bathochromic shifts were observed in
polar chlorinated solvents (CH2Cl2, C2H4Cl2, CHCl3) showing
observed for rigid-rod like π-conjugated oligomers, OH1
-OH3
and also for the digold(I) diacetylide complexes, OM1-OM3 as
emission maxima at 545-551 nm (OH3) and 562-568 nm (OM3
)
with the Stokes shift of ca. 4123-4372 cm-1 (Table S3 and S4†).
shown in Fig. 6. The solid state PL spectra for all the
6 | J. Name., 2012, 00, 1-3
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compounds were recorded as thin films spin coated on quartz
substrates, with a maximum red shift by 66 and 78 nm for OH1
and OM1 compared to its solution state (in 1,2-DCE) emission.
For OH3 and OM3, solution and solid state emission was
similar with negligible red shift. Interestingly, the PL spectra of
thin films of OH1 and its corresponding binuclear Au(I) σ-
complex are extremely broad, suggesting the possibility of
coexistence of multiple degrees of aggregations.17a It is well
documented in the literature that planar polyaromatic
compounds form aggregates in solution through π-π
interaction. The concentration dependent fluorescence
analysis of OH1-OH3 were studied in 1,2-DCE at 298 K to
Fig. 7 Normalized phosphorescence spectra of OM1-
explore self-association behaviour of the wire-like
fluorophores. At higher concentration (~10-3 M), a broad band
was observed centered at 504, 521 and 580 nm respectively
with relatively lower intensity. Upon gradual dilution emission
wavelength was blue shifted (Fig. S88†). Upon dilution beyond
10-5 M, the aggregates dissociate to form monomers exhibiting
emission at lower wavelength. The broad band at higher
concentration (10-3 M) was attributed to the self-assembled
aggregates formed through π-π interaction which becomes
predominant with increase in concentration. Being emissive as
thin film, these newly synthesized fluorenyl-alkynyl based rod-
shaped π-conjugated oligomers and their binuclear Au(I)
acetylide complexes may find application in optoelectronic
devices as the efficiency of the optoelectronic devices depends
on the solid state emission.
OM3 recorded in degassed CH2Cl2 at 77 K.
PL spectra of binuclear Au(I) complexes in 298 K and 77 K are
143, 191 and 119 nm respectively, which are in accordance
with
the
previously
reported
literature.22f-g
OM3 are 0.30, 0.23
The
phosphorescence quantum yields of OM1
-
and 0.19, which were calculated by using the absolutely
measured quantum yield of 9,10-diphenylanthracene in
degassed CH2Cl2 at 77 K.22f The emission intensity of the
organometallic wires was completely quenched while using
oxygen saturated solvent, and the phosphorescence was
reappeared by deoxygenating the solution by saturation with
argon gas, confirming that the origin of the emission is due to
triplet state (Fig. S90†). Thus, our investigation indicates that
the organic triplet emissions can be harvested by the
incorporation of Au(I) to the π-conjugated oligomers, which
enables efficient intersystem crossing from the S1 singlet to
the T1 triplet excited state. In principle, the phosphorescent
materials are superior to the fluorescent substrates for small-
molecule OLED applications as the efficiency of organic light
emitting diodes is typically controlled by the presence of
triplet state emission.
Fig. 6 Visual appearance of OH1-OH3 and OM1-OM3
demonstrating tuning of emission wavelength; (a) in 1,2-
DCE (b) in Thin film (spin-coated on quartz plate) showing
appreciable amount of emission even in solid state
(under UV illumination at 365 nm).
Lifetime. To study the dynamics of the emissive species, the
fluorescence lifetime of OH1-OH3 and their Au(I) σ-complexes
was measured in deoxygenated 1,2-DCE in the order of 10-5
M
concentration at 298 K using Time Correlated Single Photon
Counting (TCSPC) instrument. The samples were excited with
pulse laser at 408 nm. The results obtained for the π-
conjugated oligomers and the respective organometallic wires
are shown in Fig. S89† and Fig. 8 and tabulated in Table 4. A
mono-exponential decay curve was observed for the
oligomers, whereas bi-exponential decay curve was observed
for their binuclear Au(I) organometallics complexes. The
average lifetime (τav) increases on going from OH1 to OH3
(0.51, 0.98, and 3.18 ns respectively) and the similar trend is
observed for the Au(I) σ-complexes, as a result of gradual
decrease in bandgap.38 Incorporation of heavy metal caused
decrease in the fluorescence lifetime values, because of spin-
orbit coupling induced by the heavy atom resulting the mixing
of the singlet and the triplet excited states through the
efficient intersystem crossing (ISC). The phosphorescence life
time of the binuclear gold(I) complexes, measured in degassed
CH2Cl2 at 77 K, were found to be 766, 1211 and 1931 μs for
Phosphorescence. Triplet state emission (phosphorescence)
plays an important role in optoelectronics in the π-conjugated
oligomers and polymers, which is generally achieved by
incorporation of heavy metal into the π-conjugated
backbone.22f-g,29,33 The PL spectra of the synthesized digold(I)
diacetylide organometallic complexes were measured in
degassed CH2Cl2 at 77 K (Fig. 7). We observed virtually no
fluorescence band but only the spin-forbidden triplet emission
(phosphorescence) for all the organometallic wires. OM1
exhibits emission at 569 nm along with a low intense band at
614 nm, whereas OM2 exhibits broad emission centered at
653 nm. Interestingly, OM3 reveals comparatively narrow
emission band centered at 683 nm with FWHM (full width at
half maxima) of 31 nm. The role of Au(I) on inducing
phosphorescence was further confirmed by studying the
phosphorescence spectra of the parent oligomers with -C≡C-H
termini
(OH1-OH3) in similar condition, exhibiting no
phosphorescence. The difference of the emission maximum in
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OM1
Journal Name
-
OM3 respectively which are consistent with the reported application in OLEDs and other optoelectronic devices. In
Au(I) organometallic congeners.22f,38
addition, yellow phosphorescence in combination with sky
blue phosphorescence is also one of the key components for
the construction of white OLEDs. Further studies for searching
yellow light emitting materials for developing yellow and white
OLED devices is underway.
Experimental section
Materials and methods
Fig. 8 Time resolved (a) fluorescence (298 K) and (b)
All moisture sensitive reactions and manipulations were
carried out under an atmosphere of pre-purified argon or
nitrogen using dual manifold standard Schlenk techniques. The
glasswares were oven-dried (at 180 oC) and cooled under
vacuum. Tetrahydrofuran and toluene were dried over
Na/benzophenone. Dry DCM and 1,2-DCE were obtained by
distillation over CaH2 whereas MeOH and EtOH were dried by
Mg cake and stored on 3 Å molecular sieves.39 Unless
otherwise mentioned all the chemicals were of analytical
grade, obtained from Aldrich, and used without further
purification. HAuCl4 was acquired from Alfa Aesar.
Triphenylphosphine was purchased from Spectrochem and
purified by recrystallization from EtOH. Silica gel (60-120
mesh) and alumina, used for column chromatography were
purchased from Merck. Eluting systems for column
chromatography purifications were determined by thin layer
chromatography (TLC) analysis. TLC plates were visualized
under UV light (254 nm) or in iodine chamber. PdCl2 was
purchased from Arora Matthey Ltd., India. Compounds 2,7-
phosphorescence (77 K) spectra of OM1-OM3.
Table 4 Lifetime values for OM1
-OM3.
Compound
Fluorescence
lifetime, ns
Phosphorescence
lifetime, μs
a
τ1 (A1) τ2 (A2) τav
OM1
OM2
OM3
0.42
(98%)
0.73
0.99
(2%)
1.05
0.43
766
(70%) (30%) 0.83
0.85 3.12
(19%) (81%) 2.69
1211
1931
aThe average lifetime (τav) was calculated using the
equation, τav= (A1/(A1 + A2))τ1 + (A2/(A1+ A2))τ2, where A1
and A2 are the contribution from each components.
dibromo-9,9-dioctylfluorene
),41
(
3
),40
2,7-diiodo-9,9-
dioctylfluorene
(
6
2,7-Bis((trimethylsilyl)ethynyl)-9,9-
),41 2,7-diethynyl-9,9-dioctylfluorene (
42
dioctylfluorene (
7
8
),41
4,7-
Conclusions
4,7-diethynyl-2-hexylbenzotriazole
43
diethynylbenzothiadiazole (19
(
14)
and
In summary, we have successfully synthesized and
characterized a series of fluorenyl-alkynyl based D-π-A-π-D
rod-shaped oligomers with alkynyl termini and their
corresponding digold(I) diacetylide organometallic wires.
Judicious incorporation of different donor and acceptor
aromatic moieties through alkynyl spacers in between two
fluorenyl-alkynyl units allowed fine tuning of the electronic
properties. The effect of modulation of the π-conjugated
spacers was clearly revealed in their photophysical studies.
The fluorenyl-alkynyl oligomers with ─C≡CH termini and their
)
were prepared as previously
reported literature procedure (see supporting information for
detailed synthesis). Pd(PPh3)4,44 Pd(PPh3)2Cl2,45 and
Au(PPh3)Cl46 were synthesized following the procedures
described in the literature.
1H (600 MHz, 400 MHz, 200 MHz), 13C{1H} (150 MHz, 100
MHz, 50 MHz) and 31P{1H} (162 MHz) NMR spectra were
obtained from Bruker Lambda spectrometer using CDCl3 unless
otherwise mentioned. Spectra were internally referenced to
residual solvent peaks (δ = 7.26 ppm for proton and δ = 77.23
for carbon (middle peak) in CDCl3 or an externally capillary of
corresponding binuclear Au(I) complexes (OM1-OM3) are blue,
cyan and yellow emitter respectively. Thus the bandgap and
emission wavelength were finely tuned by increasing electron
deficient character of the central π-conjugated aromatic unit
(Fl, Btz and Btd) to the fluorenyl-alkynyl backbone.
Consequently, the fluorene based π-conjugated yellow emitter
was successfully achieved as targeted. The binuclear Au(I)-
alkynyl σ-complexes exhibited phosphorescence at 77 K due to
heavy atom effect by gold, enhancing efficient intersystem
crossing leading to triplet emission, as manifested by the life
time values in the range of millisecond. These phosphorescent
digold(I) diacetylide organometallic wires, specially the yellow
emissive, OH3 and OM3 are attractive building blocks for
85% H3PO4 for 31P). All coupling constants (
J) are given in Hz.
MALDI-TOF MS study was performed with DHB (2,5-dihydroxy
benzoic acid) matrix by using Bruker UltrafleXtreme
instrument. The absorption and fluorescence spectra were
collected
spectrophotometer and
spectrofluorimeter respectively. The phosphorescence spectra
were recorded on Jobin Yvon-Spex Fluorolog-3
using
a
Shimadzu
(Model
UV-2450)
a
Hitachi (Model F-7000)
a
spectrofluorimeter equipped with temperature-controlled
sample holder at 77 K in CH2Cl2. The time-resolved emission
decays were recorded using a time correlated single photon
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counting (TCSPC) picoseconds spectrophotometer (IBH). FTIR distilled EtOAc/ hexanes as eluent under inert atmosphere to
spectroscopy was recorded in Spectrum-BX (Perkin Elmer). afford an analytically pure yellow solid of OM1. Yield: 0.188 g
1
Cyclic Voltammetry (CV) and Differntial Pulse Voltammetry (88%). H NMR (CDCl3, 600 MHz): δ (ppm) 7.69-7.46 (m, 48H,
(DPV) analyses were performed on
a
BASi Epsilon HFl,Ph), 2.00-1.93 (m, 12H, octyl CH2 attached to fluorene), 1.25-
electrochemical workstation. Solid state electrochemical 1.03 (m, 60H, Hoctyl), 0.85-0.76 (m, 18H, Hoctyl), 0.67-0.54 (m,
analyses in CH3CN medium were performed on film made by 12H, Hoctyl); 13C{1H} NMR (CDCl3, 150 MHz): 151.1, 150.7, 141.2,
drop casting of the sample on a BASi glassy carbon (GC) disk 140.7, 139.3, 134.4, 134.3, 134.2, 132.2, 132.1, 131.6, 129.3,
electrode. For solution electrochemical studies, DCM was used 129.2, 129.1, 119.7, 119.6, 114.1 (aromatic carbons), 105.4 (-
as solvent. The electrochemical study was conducted using 0.1 Fl-C≡C-Au), 90.9 (-Fl-C≡C-Fl-C≡C-Fl-), 90.5 (-Fl-C≡C-Fl-C≡C-Fl-),
M
tetra-n-butylammonium hexafluorophosphate (TBAPF6) as 83.2 (-Fl-C≡C-Au), 55.4 (carbon at 9-position of Fl), 40.3, 31.5,
supporting electrolyte. The reference electrode was Ag/AgCl 30.1, 29.4, 23.8, 22.6, 14.1 (alkyl carbons); 31P{1H} (CDCl3, 162
and the auxiliary electrode was
Pt wire. The MHz): 42.7 ppm; FTIR (KBr, cm-1): 2204 (υC≡C stretching); MALDI-
a
ferrocene/ferrocenium couple occurs at E1/2 = +0.51 (70) V TOF MS (m/z): C131H150Au2P2; Calculated 2180.062 ([M+H]+);
versus Ag/AgCl under the same experimental conditions. Experimental 2180.158 ([M+H]+); Anal. Calc. for C131H150Au2P2:
Thermogravimetric analysis (TGA) was carried out using a C, 72.16; H, 6.93. Found: C, 65.24, H, 7.24. UV-Vis λmax: 391 nm
Perkin Elmer Pyris Diamond TG/DTA instrument. The thermal (ε = 10.39×104 M-1cm-1); λem(λex): 426 (391) nm. In elemental
stabilities of the samples under nitrogen were determined by analysis of OM1, even after repeated attempt, identical result
measuring their weight losses while heating at a rate of 5 was observed with 6.9 % less in ‘C’ (See SI). This is presumably
oC/min. Differential scanning calorimetry (DSC) was performed due to the formation of Au particles embedded in the carbon
on a TA DSC Q20 unit operated at a heating and cooling rates matrix (generated from fluorenyl-alkynyl moieties).
of 10 oC/min. Elemental analysis was carried out in Perkin
Synthesis of OM2. OM2 was prepared using a similar procedure
Elmer Series II CHN 2400 analyzer.
as that for OM1 using OH2 (125 mg, 0.12 mmol), Au(PPh3)Cl
(119 mg, 0.24 mmol) and NaOMe (31 mg, 0.58 mmol in 5 mL of
dry MeOH). It was purified by a short (column height 5 cm and
diameter 18 mm) alumina column using degassed and distilled
Pertinent crystallographic data (Table S8†) for O3 including
X-ray data collection and refinement detail have been
summarized in SI. The orange needle-like single crystals of O3
suitable for X-ray crystallography, were obtained by layering EtOAc/ hexanes as eluent under inert atmosphere to get
analytically pure dark yellow solid of OM2. Yield: 0.212 g
(92%). H NMR (CDCl3, 600 MHz): δ (ppm) 7.65-7.47 (m, 44H,
HBtz, Fl, Ph), 4.85-4.83 (t, J= 6 Hz, 2H, (Btz)N-CH2-C5H11), 2.23-2.21
MeOH on DCM solution of O3. The title compound crystallizes
in the triclinic space group, P-1. Two independent molecules of
O3 were located in the asymmetric unit with negligible
differences in their metrical parameters.47 CCDC 1512387
contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The
1
(m, 2H, (Btz)-N-CH2-CH2-C4H9) 1.96-1.93 (m, 8H, octyl CH2
attached to fluorene), 1.25-1.02 (m, 46H, Hhexyl, octyl), 0.82-0.80
(m, 15H, Hhexyl, octyl), 0.61-0.56 (m, 8H, Hoctyl); 13C{1H} (CDCl3,
150 MHz): 151.1, 150.8, 144.3, 141.7, 139.2, 134.4, 131.6,
131.3, 130.1, 129.1, 127.1, 126.2, 123.8, 120.9, 119.7, 113.8
(aromatic carbons), 105.4 (-Fl-C≡C-Au), 105.2 (-Fl-C≡C-Btz-C≡C-
Fl-), 97.7 (-Fl-C≡C-Btz-C≡C-Fl-), 85.5 (-Fl-C≡C-Au), 57.1 ((Btz)N-
CH2-C5H11), 55.2 (carbon at 9-position of Fl), 40.6, 31.8, 31.3,
30.2, 30.1, 29.4, 29.3, 23.8, 22.6, 22.5, 14.1, 13.9 (alkyl
carbons); 31P{1H} (CDCl3, 162 MHz): 42.7 ppm; FTIR (KBr, cm-1):
2200 (υC≡C stretching); MALDI-TOF MS (m/z): C114H125Au2N3P2;
Calculated 1992.875 ([M+H]+); Experimental 1992.790
([M+H]+); Anal. Calc. for C114H125Au2N3P2: C, 68.70; H, 6.32, N,
2.11. Found: C, 67.48, H, 6.66, N, 2.36. UV-Vis λmax: 410 nm (ε =
6.64×104 M-1cm-1); λem(λex): 462 (410) nm.
Synthesis of OM3. OM3 was synthesized analogously to OM1
using OH3 (157 mg, 0.16 mmol), Au(PPh3)Cl (162 mg, 0.33
mmol) and NaOMe (42 mg, 0.78 mmol in 6 mL of dry MeOH). It
was purified by a short (column height 6 cm and diameter 18
mm) alumina column using degassed and distilled EtOAc/
hexanes as eluent under inert atmosphere to afford pure red
solid of OM3. Yield: 0.275 g (91%). 1H NMR (CDCl3, 600 MHz): δ
(ppm) 7.83 (s, 2H, HBtd), 7.67-7.47 (m, 42H, HFl, Ph), 1.97-1.94
(m, 8H, octyl CH2 attached to fluorene), 1.25-1.02 (m, 40H,
Hoctyl), 0.82-0.80 (m, 12H, Hoctyl), 0.66-0.55 (m, 8H, Hoctyl);
13C{1H} NMR (CDCl3, 150 MHz): 154.6, 151.4, 151.1, 142.3,
139.4, 134.6, 132.7, 130.9, 131.8, 130.2, 129.8, 129.4, 129.3,
127.4, 126.4, 120.7, 120.0, 117.4 (aromatic carbons), 105.5 (-
Fl-C≡C-Au), 105.4 (-Fl-C≡C-Btd-C≡C-Fl-), 99.2 (-Fl-C≡C-Btd-C≡C-
Fl-), 85.7 (-Fl-C≡C-Au), 55.4 (carbon at 9-position of Fl), 40.8,
32.0, 30.3, 29.6, 24.0, 22.8, 14.3 (alkyl carbons); 31P{1H} (CDCl3,
Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
Synthesis and characterization
Synthesis and characterization of the key precursors and
oligomers having -C≡C-TMS (O1-O3) and -C≡C-H termini (OH1-
OH3) are included in supporting information.†
Synthesis of OM1. OH1 (124 mg, 0.098 mmol) and
Au(PPh3)Cl (102 mg, 0.21 mmol) were dissolved in 10 mL of dry
DCM in a 100 mL Schlenk flask under argon atmosphere. To
that NaOMe (26 mg, 0.49 mmol in 5 mL of dry MeOH) was
added through a syringe. The reaction flask was covered with
aluminium foil to protect it from light. The reaction mixture
o
was stirred for overnight at 28 C under argon atmosphere. It
was filtered through celite bed (2 cm height and 18 mm
diameter) by using a Schlenk frit under argon atmosphere to
remove NaCl. The solvent was evaporated under reduced
pressure and dissolved in minimum amount of dry DCM (2
mL). The compound was precipitated from its concentrated
CH2Cl2 solution by adding dry MeOH (20 mL) under stirring. A
bright yellow precipitate was obtained, which was separated
by filtration through a filter-paper-stripped cannula. Finally,
the precipitate was purified by a short (column height 6 cm
and diameter 18 mm) alumina column using degassed and
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162 MHz): 42.9 ppm; FTIR (KBr, cm-1): 2200 (υC≡C stretching);
MALDI-TOF MS (m/z): C108H112Au2N2P2S; Calculated 1925.743
([M+H]+); Experimental 1925.690 ([M+H]+); Anal. Calc. for
C108H112Au2N2P2S: C, 67.35; H, 5.86, N, 1.45. Found: C, 67.21, H,
6.04, N, 2.13. UV-Vis λmax: 453 nm (ε = 3.32×104 M-1cm-1);
λem(λex): 564 (453) nm.
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Acknowledgements
SKP acknowledges the financial support from the DST-SERB,
India through Fast Track scheme (SB/FT/CS-010/2012). SKP
thanks IIT Kharagpur (IIT KGP) for funding the purchase of an
electrochemical workstation through Competitive Research
Infrastructure Seed Grant (IIT/SRIC/CHY/PBR/2014-15/44,
SGIRG). SNI thanks UGC, and AS acknowledges IIT KGP for
doctoral fellowship. Dr. R. Natarajan (IICB, Kolkata) is gratefully
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acknowledged for his help in solving the X-ray structure of O3
.
Authors thank Prof. N. Sarkar’s group (IIT KGP) for providing
TCSPC facilities. Prof. M. Halder and Mr. Sudipta Panja (IIT
KGP) are acknowledged for helping in phosphorescence
measurement. Authors also acknowledge Central Research
Facility, IIT KGP for providing analytical facilities.
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Dalton Transactions
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DOI: 10.1039/C7DT00895C
TOC
Yellow light emitting fluorenyl-alkynyl based D-π-A-π-D
rod-shaped oligomer with alkynyl termini, and the
corresponding binuclear Au(I) organometallic wire are
achieved by fine tuning of the bandgap through
systematic modulation of the π-conjugated spacers.