Anthracene derived dinuclear gold(I) diacetylide complexes: Synthesis, photophysical properties and supramolecular interactions

Article abstract of DOI:10.1016/j.jorganchem.2016.04.013

New anthracene derived dinuclear Au(I)-diacetylide complex (1) has been synthesized in which two Au(I) units are attached at 9,10- positions of ethynyl anthracene moiety. 1 exhibits rare non-covalent intermolecular Au?H-C interactions, leading to the formation of a supramolecular 2D-network. Further, to understand the effect of CCAuPPh₃ units at different position, complexes (2) and (3) were synthesized, where CCAuPPh₃ units are attached to 2,6- and 1,8- positions of anthracene, respectively. The absorption and emission spectra of 1-3 have been studied and surprisingly 1 was found to be highly fluorescent with high quantum yield compared to 2 and 3, this may be due to more perturbation of Au(I) on π system. Complexes 1-3 have been characterized by elemental analysis, NMR and Mass spectroscopy and authenticated by their single-crystal X-ray structures.

Full text of DOI:10.1016/j.jorganchem.2016.04.013

Accepted Manuscript
Anthracene derived dinuclear gold(I) diacetylide complexes: Synthesis, photophysical
properties and supramolecular interaction
Veenu Mishra, Abhinav Raghuvanshi, Anoop Kumar Saini, Shaikh M. Mobin
PII:
S0022-328X(16)30156-5
10.1016/j.jorganchem.2016.04.013
JOM 19469
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 1 February 2016
Revised Date: 1 April 2016
Accepted Date: 12 April 2016
Please cite this article as: V. Mishra, A. Raghuvanshi, A.K. Saini, S.M. Mobin, Anthracene derived
dinuclear gold(I) diacetylide complexes: Synthesis, photophysical properties and supramolecular
interaction, Journal of Organometallic Chemistry (2016), doi: 10.1016/j.jorganchem.2016.04.013.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical abstract
Three anthracene based binuclear Au(I) complex was synthesized and characterized, out of
three 1 was found to be highly fluorescent with good quantum yield and also exhibits non-
covalent intermolecular Au···H−C interactions, leads to the formation of unique
supramolecular 2D-network.

ACCEPTED MANUSCRIPT
Anthracene derived dinuclear gold(I) diacetylide complexes: synthesis, photophysical
properties and supramolecular interaction
Veenu Mishra,a Abhinav Raghuvanshi,b Anoop Kumar Saini,a Shaikh M. Mobin*a.
a Discipline of Chemistry, Indian Institute of Technology Indore, Simrol, Indore 452020, India.
b Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India.
Email: xray@iiti.ac.in
Phone No: +919713030406
1

ACCEPTED MANUSCRIPT
Abstract
New anthracene derived dinuclear Au(I)-diacetylide complex (1) has been synthesized in which
two Au(I) units are attached at 9,10- positions of ethynyl anthracene moiety. 1 exhibits rare non-
covalent intermolecular AuꢀꢀꢀH−C interactions, leading to the formation of a supramolecular 2D-
network. Further, to understand the effect of C≡CAuPPh3 units at different position, complexes
(2) and (3) were synthesized, where C≡CAuPPh3 units are attached to 2,6- and 1,8- positions of
anthracene, respectively. The absorption and emission spectra of 1-3 have been studied and
surprisingly 1 was found to be highly fluorescent with high quantum yield compared to 2 and 3,
this may be due to more perturbation of Au(I) on π system. Complexes 1−3 have been
characterized by elemental analysis, NMR and Mass spectroscopy and authenticated by their
single-crystal X-ray structures.
Keywords: Anthracene, Gold(I) diacetylide, Fluorescence, Intermolecular AuꢀꢀꢀH−C
interactions.
2

ACCEPTED MANUSCRIPT
Introduction
Polyaromatic hydrocarbons (PAHs) with extended conjugation have gained much
attention in past decades due to their strong visible π-π* absorption, intense luminescence and
high charge mobility in the solid state [1-3]. They have got applications in advanced materials
for organic light-emitting diodes (OLEDs), field-effect transistors (FETs) and solar cells [4-5].
Connecting PAH to the metal center through the alkyne unit as a spacer introduces additional
features to be used as molecular wires, nonlinear optical materials and molecular electronics [6-
8]. It is well known that metallation of PAH ring system has significant effect on its
photophysical properties and structural dimensionalities [9-14].
Alkynyl gold complexes have drawn considerable interest in recent years [15] because of
their aurophilic properties, exciting photophysical properties and their ability to build
supramolecular array [16-17]. Recent reports on PAH linked with platinum(II) and gold(I) via
the alkynyl spacer show interesting structural property, photophysical properties and their
structural reactivity [18-23]. The organoAu(I) system shows enhanced luminescent properties
for alkynylAu(I) phosphines complexes compared to other gold complexes [24-33].
Non-covalent interactions are the primary driving force in constructing supramolecular
architectures as well as in determining the constitution and conformation of molecules.
Although, in gold chemistry extensive literatures are available to understand the aurophilic
interaction (AuꢀꢀꢀAu) [34], however, the non-covalent AuꢀꢀꢀH−C interactions are less explored
[35-37]. The AuꢀꢀꢀH−C interactions are mainly observed in Au(I) phosphine and thione
complexes where gold atoms are in almost linear geometry and leaving behind coordination site
for gold hydrogen interactions. Usually, AuꢀꢀꢀH−C contacts in Au(I) complexes are
3

ACCEPTED MANUSCRIPT
intramolecular in nature and in case of intermolecular AuꢀꢀꢀH−C interactions they are restricted to
supramolecular 1D-chain [38-48].
Herein we report the synthesis, characterization and photophysical properties of a series
of three new anthrylAu(I) diacetylide, 1-3 complexes in which the Au(I) acetylide units are
attached at 9,10-, 2,6- and 1,8-positions of anthracene. 1 display more red shift and stronger
fluorescence with high quantum yield probably due to more perturbation of Au(I) on π system in
1 compared to 2 and 3. Additionally, the single crystal studies of 1-3 reveal that 1 shows rare
noncovalent intermolecular AuꢀꢀꢀH−C interactions that leads to the formation of a supramolecular
2D-network, whereas, in 3 intramolecular AuꢀꢀꢀH−C interactions have been observed.
4

ACCEPTED MANUSCRIPT
Results and Discussion
1 was synthesized by reaction of 2 mol equivalent of PPh3AuCl with ethynyl anthracene
at 9,10-positions in presence of NaOEt in ethanol (Scheme 1). Compound 1 was characterized by
various spectroscopic techniques. UV/Vis absorption and emission spectra of 1 reveals high
fluorescence property with excellent quantum yield. Single crystal X-ray diffraction studies of 1,
indicate the existence of intermolecular AuꢀꢀꢀH−C interactions creating a supramolecular 2D-
network.
1 was crystallized in P21/n space group, with crystallographically imposed inversion
center (Figure 1 and Table S1). In 1, the C≡CAuPPh3 units are attached to the planar anthracene
ring at the 9,10-positions. The Au−P and Au−C distances of 2.281(1) Å and 2.004(5) Å,
respectively, are similar to that reported for aryl Au(I) phosphine complexes (Table S2) [49-50].
The slight deviation from linearity has been observed in P-Au-C angle of 175.1(2)° in 1,
consequently the C≡C (C1−C2) bond lies 4° out of the anthracene plane.
It is interesting to note that the linear coordination geometry around Au(I) in 1 makes it
susceptible for additional non-covalent interactions. The packing diagram of 1 reveals that the
coordination environment of Au(I) is extended further by an intermolecular AuꢀꢀꢀH−C interaction
between the metal ion and one of the aromatic hydrogens of PPh3 of adjacent molecule
Au(1)ꢀꢀꢀH(11)−C(11) 2.87 (1) Å with the Au(1)ꢀꢀꢀH(11)−C(11) bond angle of 171.00(1)°. It has
been observed that neighboring molecules link together through these interactions along the b-
axis, yielding one-dimensional polymeric chain [51]. This 1D chain further extends via the same
AuꢀꢀꢀH−C interactions along the c-axis, forming herringbone like 2D-network. Thus, both the
gold atoms in 1 are involved in AuꢀꢀꢀH−C supramolecular interactions (Figure 2, S1 and S2).
5

ACCEPTED MANUSCRIPT
The considerably short AuꢀꢀꢀH−C bond distance and larger AuꢀꢀꢀH−C bond angle develop
regular directionality, which suggest that these interactions are hydrogen bonding in nature [43-
45]. To the best of our knowledge, 1 represents the first example of supramolecular 2D-network
involving intermolecular AuꢀꢀꢀH−C non-covalent interactions.
The above interesting features show the influence (if any) of the binding of C≡CAuPPh3
at the 9,10-positions of the anthracene moiety towards the formation of 2D-network via
AuꢀꢀꢀH−C interactions. This prompted us to synthesized similar complexes by varying the
position of alkynyl group attached to anthracene such as 2,6- and 1,8-positions. In this regard, we
obtained compounds 2 and 3 with the linkage of C≡CAuPPh3 at 2,6- and 1,8-positions (Scheme
2).
Complexes 2 and 3 were synthesized by following the same procedure as of 1 and along
with usual spectroscopic techniques analysed by UV/Vis absorption/fluorescence spectra and
were established to be fluorescent albeit less than 1. Both compounds were further analysed by
single crystal X-ray diffraction studies ensuing the presence of πꢀꢀꢀπ and CHꢀꢀꢀπ interactions in 2
while intramolecular AuꢀꢀꢀH−C interaction in 3.
2 and 3 were crystallized in Pī and P212121 space group, respectively, (Figure 3, 4 and
Table S1). 2 shows a planar anthracene ring on which C≡CAuPPh3 units are attached to its 2,6-
position. Unlike 2, where substitutions were at trans positions, in 3, the C≡CAuPPh3 units are
attached to its 1,8- position i.e. cis-position to the planar anthracene ring. The distance between
Au–P and Au–C are 2.275(5) Å, 2.00(2) Å in 2, and 2.271(7) Å, 2.282(6) Å, 1.94(3) Å, in 3
respectively (Table S2). Which are similar to the reported arylAu(I) phosphine complexes. The
P–Au–C and Au–C–C angles in 2 were found to be 176.9(4)° and 172.4(17)° which suggest
6

ACCEPTED MANUSCRIPT
slightly distorted geometry around Au(I) from linearity. The C≡C (C1–C2) bonds in 2 and 3
were also slightly deviated from the anthracene plane by 5° and 2°, respectively. Compound 3
found to be highly strained due to the presence of bulky PPh3 groups at cis position which results
both the Au(I) centers to move slightly outward and tilted from the anthracene plane (Table S2).
The packing diagram of 2 reveals the existence of CHꢀꢀꢀπ and πꢀꢀꢀπ interactions. CHꢀꢀꢀπ
interactions involve H(13) of phenyl ring of PPh3 unit and π electrons of acetylenic bond,
forming a wave like 1D polymeric chain (Figure 5 and S3). The packing features of 3 establishes
intramolecular AuꢀꢀꢀH−C interactions involving hydrogens of PPh3, where AuꢀꢀꢀH−C bond
distances and bond angles are Au(2)−H(48) 3.01(1) Å, Au(2)−H(54) 2.86 (1)Å, Au(1)−H(20)
3.00 (1) Å and Au(2)−H(54)-C(54) 123.00(1)°, Au(2)−H(48)-C(48) 118.31(1)°, Au(1)−H(20)-
C(20) 111.66(1)° (Figure 6).
Unlike 1 or 2, the observed intramolecular AuꢀꢀꢀH−C interactions in 3, originate due the
cis orientation of C≡CAuPPh3 moieties. The steric repulsion between the two PPh3 groups in the
cis orientation facilitates the C−H of the phenyl ring to move closer to the gold. The packing of 3
is further extended by C−Hꢀꢀꢀπ, interactions C(4)−H(34) ꢀꢀꢀπ 3.359 Å, resulting in 1D polymeric
chain (Figure 7, and S4). The synthesis of 3 found to be unique, as to the best of our knowledge
there are no reports of 1,8-anthracenyl complexes with bulky PPh3 group substitution at Au(I)
center. So far only few reports of 1,8-anthracenyl substituted Pd(II) / Pt(II) complexes with less
bulkier triethyl phosphine group at Pd(II) center have been reported [52-55].
The absorption and emission spectroscopic studies of complexes 1-3 and their respective
ligands were recorded in CH2Cl2 (1.0 x 10-5 M) at room temperature (Figure 8, 9, S5-S6 and
Table 1, S3). 1-3 complexes display two absorption bands (i) with a broad intense vibronic band
7

ACCEPTED MANUSCRIPT
between 320−470 nm (A), and (ii) very intense, band between 265−310 nm (B). Since the spectra
of anthracene and diethynyl anthracene display similar absorption patterns, the absorption bands
are assigned to π → π* transitions primarily localized in the anthracene. The absorption bands of
+
anthracene are due to the LUMO ← HOMO (1B1u ← 1Ag), LUMO ← HOMO-1 (1B2u ←1Ag),
LUMO+1 ← HOMO (1B2u- ← 1Ag), The second and third transitions lead to the two degenerate
1B2u excited states, which undergo strong configuration interaction to give the high-energy
1
+
1
−
“plus” state B2u and the low-energy “minus” state B2u . The very intense band at around 250
nm corresponds to the (1B1u+ ← 1Ag) transition. Whereas the transition (1B1u- ← 1Ag) is slightly
1
1
-
higher in energy than the (1B1u← Ag) transition (1B1u is lower than B2u by ∼1500 cm-1) is
forbidden (ε ≈ 10 M-1 cm-1) and hidden under the latter.[ 10, 56]
Though the symmetries of the Au(I) complexes and anthracene are quite different, still
there exist a similarity between absorption bands displayed by the complexes and the electronic
transitions of anthracene. Band A in the spectra of the complexes corresponds to the LUMO ←
HOMO (1B1u ← 1Ag) transition, which is also known as an S0 → S1 transition. The intense band
B correspond to the transition to the “plus” state 1B2u+ (1B2u+ ← 1Ag).
The transition is significantly intensified in the spectra of the complexes, indicating that
the electronic structure of the anthracenyl ring is significantly perturbed by the Au(I) ions and
the ethynyl groups.[10, 57] Further, absorption bands of complexes 1, 2 and 3 are found to be
red shifted compared to respective ligands. Absorption maxima of 1 shows red shifts of ~50 nm
compare to 2 and 3, which indicates that substituents have more perturbation on the anthracenyl
rings when they are at 9,10 position. In case of 2 and 3 the bands are observed almost in the same
range. In addition to this, complexes display intense absorption in near-UV region. 2 shows a
8

ACCEPTED MANUSCRIPT
intense absorption band at 310 nm whereas in 1 and 3 show around 274 and 267 nm, similar to
that of previously reported complexes [12].
Complexes 1-3 were found to be emissive in solution as their respective ligands. On excitation of
complexes 1, 2 and 3 at 434 nm, 389 nm and 398 nm, respectively, they display similar emission
pattern to their corresponding ligands (Figures 9 and S6. Table S3). The fluorescence of the
complexes 1 and 3 were found to be red shifted from their respective ligands around 15-20nm
while marginal blue shift (5nm) is observed in complex 2. Emission spectra of 1 shows very
strong fluorescence with quantum yield of 0.89 compared to 2 and 3 (quantum yield = 0.02 for 2
and 0.04 for 3). 1 shows high fluorescence probably due to the substitution at 9,10 position
which is in contrast with 2 and 3 [58-59]. Complex 1 also shows emissive nature in solid-state
(Figure S7).
Table 1. Absorption and emission spectroscopic details of 1, 2 and 3.
Emission
λmax
(nm)
Emission
Life Time
(τ)ns
Quantum
yield
S.
No
Absorption λmax nm 10-5/ɛ max (cm-
1, M-1)
Φ
462(1.01), 434(0.781), 410(0.387),
275(1.87), 230(2.07)
499
4.06
0.89
1
412(1.17), 389(1.36),
366(0.897), 310(8.77), 238(4.30)
445
455
4.02
0.57
0.02
2
3
422(.976), 398(.936), 376(.583),
267(5.67), 228(4.69)
0.038
To get an insight into the nature of electronic transitions, density-functional theory (DFT)
and time dependent density-functional theory (TDDFT) calculations were performed with the
Gaussian09 program package [60]. All the calculations were performed at B3LYP [61-62] level
9

ACCEPTED MANUSCRIPT
of theory using the Stuttgart/Dresden effective core potential (SDD) basis set [63] for the gold
atoms and 6-31G** basis set [64] for remaining atoms. Geometries were optimized without
imposed symmetry or other restraints. On the basis of the ground state optimized geometries,
TD-DFT calculations were performed in presence of dichloromethane using the conductive
polarizable continuum model (CPCM) [65-66].
In all three cases, the calculated bond distances for the optimized structures are in good
agreement to those obtained in their crystal structures (Figure S8, S9 and S10). For all three
complexes, the highest-occupied molecular orbitals (HOMOs) are π-type MOs while the lowest-
occupied molecular orbitals (LUMOs) are π*-type, delocalized on the anthracene unit. The TD-
DFT predicted spectra are in good agreement with the experimental data and clearly suggest that
the band observed in the visible range is dominated by HOMO to LUMO excitation (Figure
S11). Further, in comparison to 2,6- and 1,8- derivative, there is red-shift in case of 9,10-
anthracene derivative, which is supported by calculations as the calculated HOMO-LUMO gaps
are 0.102 eV, 0.117 eV and 0.115 eV for 1, 2 and 3 respectively (Figure 10 and S11). Since
perturbation on anthracene lower the symmetry of the π-system which leads to a bathochromic
shift in HOMO to LUMO transition, the results suggest that substituents have more perturbation
on the anthracenyl rings when they are at 9,10 position.
Conclusion
In summary, complex 1 with C≡CAuPPh3 moieties attached to the 9,10-positions of
anthracene selectively yields the strong fluorescent, rare 2D-network feature via intermolecular
AuꢀꢀꢀH−C interactions. However, the analogous compounds 2 and 3 with C≡CAuPPh3 moieties
attached to the 2,6- and 1,8- positions of anthracene result in weakly fluorescent 1D-polymeric
10

ACCEPTED MANUSCRIPT
chain via C−Hꢀꢀꢀπ and πꢀꢀꢀπ interactions and intramolecular AuꢀꢀꢀH−C interactions, respectively.
The present work thus highlights the AuꢀꢀꢀH−C interactions as well as the impact of linkage of
Au(I) acetylide groups at the selective sites of the planar anthracene on the photophysical
properties.
11

ACCEPTED MANUSCRIPT
Experimental
General Methods: All manipulations were carried out at room temperature under a nitrogen
atmosphere. Solvents were predried, distilled and degassed prior to use, except those for
spectroscopic measurements, which were of spectroscopic grade. The starting materials 9,10-
dibromoanthracene, 1,8-diiodoanthracene and AuPPh3Cl were commercially available. The
starting material 2,6-diiodoanthracene was prepared by the procedures described in the literature
[67] 9,10-Bis((trimethylsilyl)ethynyl) anthracene, [59, 68-70] 2,6-Bis((trimethylsilyl)ethynyl)
anthracene,[59,71]
1,8-Bis((trimethylsilyl)ethynyl)
anthracene,[59,72-73]
and
their
corresponding acetylenes were synthesized by earlier reported method [27].
Instruments: Elemental analyses were carried out with a Flash 2000 elemental analyzer.
UV/Vis absorption and emission spectra were recorded on a Cary-100 Bio UV−Vis
spectrophotometer and a Horiba Jobin-Yvon Floromax 4P spectrophotometer respectively. 9,10-
bis(phenylethynyl) anthracene was used as a standard in measuring the quantum yields. 1H NMR
31
and P NMR spectra were recorded on Bruker Avance(III) 400MHz spectrometer. HRMS was
recorded on a Brucker-Daltonics, micrOTOF-Q II mass spectrometer. Single-crystal X-ray
structural studies were performed on an Agilent Technology Supernova CCD diffractometer
equipped with a low-temperature attachment.
X-ray Crystallography
Data were collected at 150 K for 2 and at 293 K for 1 and 3 using graphite-monochromated Mo
Kα (λα = 0.71073 Å) and Cu Kα (λα =1.54814 Å). The strategy for data collection was evaluated
using the CrysAlisPro CCD software. The data were collected by the standard φ−ω scan
techniques and scaled and reduced using CrysAlisPro RED software. The structures were solved
12

ACCEPTED MANUSCRIPT
by direct methods using SHELXS-97 and refined by full-matrix least squares with SHELXL-97
on F2 [74]. The positions of all of the atoms were obtained by direct methods. All non-H atoms
were refined anisotropically. In 3 SQUEEZE was applied by using platon programme to remove
3 disorder chloroform solvent molecules. All Hydrogen atoms were placed in geometrically
constrained position and refined with isotropic temperature factors, generally 1.2 X Ueq of their
parent atoms. Moreover, despite several attempts we could not get better quality of crystals for 2
and 3. All the short contacts and interactions, mean-plane analyses, and molecular drawings were
obtained using the Diamond program (version 3.1d) and Mercury (v 3.5.1). The crystal and
refinement data are summarized in Table S1, and selected bond distances and angles are shown
in Table S2.
(1) Synthesis of (Ph3PAuI)2-9,10-anthracenyldiacetylide 1.
To a suspension of Ph3PAuCl (100 mg, 0.20 mmol) in ethanol (20 ml) NaOEt, freshly prepared
from sodium (4.87 mg, 0.21 mmol) in ethanol (5 ml) and 9,10- bis (ethynyl anthracene) (22.6
mg, 0.10 mmol) were added. The solution was refluxed for 1 h, cooled and concentrated after
which a yellow precipitate formed. The yellow colored solid was isolated by simple filtration
method. The precipitate was further washed with ethanol and dried at room temperature to afford
1. X-ray quality crystals of 1 were obtained from CHCl3/ hexane at room temperature. Yield:
1
60% Anal Calcd for 1 (C54H38Au2P2) C 56.76, H 3.35. Found: C 56.81, H 3.05 H NMR (400
MHz, CDCl3) δ = 8.86 (dd, J=3.2, 4H ant), 7.49-7.65(m, 34H anth and PPh3), 13C NMR (100
MHz, CDCl3) δ = 96.51, 125.73, 128.17, 129.14, 129.26, 131.58, 132.79, 134.36, 134.49, 31P
NMR (165.561 MHz, CDCl3) 42.38 s ESI-MS: 1142[M].
(2) Synthesis of (Ph3PAuI)2-2,6-anthracenyldiacetylide 2.
13

ACCEPTED MANUSCRIPT
Complex 2 was synthesizes by following the same method as 1 using 2,6-bis(
ethynylanthracene). Light yellow color crystals of 2 were grown in CH2Cl2/hexane at room
temperature. Yield: 38% Anal Calcd for 2 (C54H38Au2P2) C 56.76, H 3.35. Found: C 57.12, H
1
2.89 H NMR (400 MHz, CDCl3) δ = 8.22(s, 2H ant), 8.13( s, 2H ant), 7.85 (d, J= 10.28, 2H
ant), 7.45-7.60(m, 32H ant and PPh3), 13C NMR (100 MHz, CDCl3) δ = 91.92, 125.56, 127.71,
129.13, 129.24, 129.35, 130.72, 131.58, 131.93, 134.29, 134.43, 31P NMR (165.561 MHz,
CDCl3) 42.31 s ESI-MS: 1142[M].
(3) Synthesis of (Ph3PAuI)2-1,8-anthracenyldiacetylide 3.
Complex 3 was synthesizes by following the method described above for 1 using 1,8-bis(
ethynyl anthracene). Golden yellow color crystals of 3 were grown in CHCl3/hexane at room
temperature. Yield: 48% Anal Calcd for 3 (C54H38Au2P2) C 56.76, H 3.209. Found: C 57.01, H
1
3.508 H NMR (400 MHz, CDCl3) δ = 9.83(s 1H anthracene), 8.35 (s 1H anthracene) 7.86 (d,
13
J= 8.5, 2H ant), 7.80 (d, J= 6.7, 2H ant), 7.54-7.47(m, 32H ant and PPh3), C NMR (100 MHz,
CDCl3) δ = 87.56, 124.96, 126.90, 127.22, 129.01, 129.12, 130.35, 131.34, 131.57, 132.07,
134.33, 134.46, 31P NMR (165.561 MHz, CDCl3) 42.19 s ESI-MS: 1165[M + 23].
Acknowledgements
We are grateful for the use of the Single Crystal X-ray diffraction facility at the Sophisticated
Instrumentation Centre (SIC), IIT Indore. SMM thanks CSIR, New Delhi, for a research grant.
14

ACCEPTED MANUSCRIPT
References
[1] J. Zaumseil, H. Sirringhaus, Chem. Rev. 107 (2007) 1296.
[2] S.-C. Lo, P.L. Burn, Chem. Rev. 107 (2007) 1097.
[3] J.E. Anthony, Angew. Chem. Int. Ed. 47 (2008) 452.
[4] R. Ruiz, D. Choudhary, B. Nickel, T. Toccoli, K.-C. Chang, A.C. Mayer, P. Clancy, J.M.
Blakely, R.L. Headrick, S. Iannotta, G.G. Malliaras. Chem. Mater. 16 (2004) 4497.
[5] M. Bendikov, F. Wudl, D.F. Perepichka, Chem. Rev. 104 (2004) 4891.
[6] D.W. Bruce, D.O. Hare, Inorganic Materials, John Wiley & Sons Ltd, Chichester, 1996.
[7] N.J. Long, Angew. Chem. Int. Ed. 34 (1995) 21.
[8] N.J. Long, C.K. Williams, Angew. Chem. Int. Ed. 42 (2003) 2586.
[9] M.-H. Nguyen, J.H.K. Yip, Organometallics 29 (2010) 2422
[10] J. Hu, R. Lin, J.H.K. Yip, K.-Y. Wong, D.-L. Ma, J.J. Vittal, Organometallics 26 (2007)
6533.
[11] J. Hu, J.H.K. Yip, D.-L. Ma, K.-Y. Wong, W.-H. Chung, Organometallics 28 (2009) 51.
[12] J. Hu, H. Xu, M.-H. Nguyen, J.H.K. Yip, Inorg. Chem. 48 (2009) 9684.
[13] W.Y. Heng, J. Hu, J.H.K. Yip, Organometallics 26 (2007) 6760.
[14] B.-Y. Wang, A.R. Karikachery, Y. Li, A. Singh, H.B. Lee, W. Sun, P.R. Sharp, J. Am.
Chem. Soc. 131 (2009) 3150.
15

ACCEPTED MANUSCRIPT
[15] L.-L. Hung, W.H. Lam, K.M.-C. Wong, E.C.-C. Cheng, N. Zhu, V.W.-W. Yam, Inorg.
Chem. Front. 2 (2015) 453.
[16] V.W.-W. Yam, E.C.-C. Cheng, Top. Curr. Chem. 281 (2007) 269.
[17] V.W.-W. Yam, E.C.-C. Cheng, Chem. Soc. Rev. 37 (2008) 1806.
[18] J. Hu, R. Lin, J.H.K. Yip, K.-Y. Wong, D.-L. Ma, J.J. Vittal, Organometallics 26 (2007)
6533.
[19] J. Hu, J.H.K. Yip, D.-L. Ma, K.-Y. Wong, W.-H. Chung, Organometallics 28 (2009) 51.
[20] J. Hu, H. Xu, M.-H. Nguyen, J.H.K. Yip, Inorg. Chem. 48 (2009) 9684.
[21] J. Hu, J.H.K. Yip, Organometallics 28 (2009) 1093.
[22] W.-Y. Wong, C.-L. Ho, Coord. Chem. Rev. 250 (2006) 2627
[23] M.-H. Nguyen, J.H.K. Yip, Organometallics 29 (2010) 2422.
[24] T. Müller, S.W.K. Choi, D.M.P. Mingos, D. Murphy, D.J. Williams, V.W.-W. Yam, J.
Organomet. Chem. 484 (1994) 209.
[25] V.W.-W. Yam, S.W.K. Choi, J. Chem. Soc., Dalton Trans. (1996) 4227.
[26] V.W.-W. Yam, S.W.K. Choi, K.K. Cheung, Organometallics 15 (1996) 1734.
[27] H. Xiao, K.K. Cheung, C.M. Che, J. Chem. Soc. Dalton Trans. (1996) 3699.
[28] M.J. Irwin, J.J. Vittal, R.J. Puddephatt, Organometallics 16 (1997) 3541.
[29] V.W.-W. Yam, K.L. Cheung, L.H. Yuan, K.M.C. Wong, K.K. Cheung, Chem. Commum.
16 (2000) 1513.
[30] V.W.-W. Yam, S.K. Yip, L.H. Yuan, K.L. Cheung, N. Zhu, K.K. Cheung, Organometallics
22 (2003) 2630.
16

ACCEPTED MANUSCRIPT
[31] V.W.-W. Yam, K.L. Cheung, S.K. Yip, K.K. Cheung. J. Organomet. Chem. 681 (2003)
196.
[32] V.W.-W. Yam, K.L. Cheung, E.C.C. Cheng, N. Zhu, K.K. Cheung, J. Chem. Soc. Dalton
Trans. (2003) 1830.
[33] W. Lu, N. Zhu, C.M. Che, J. Am. Chem. Soc. 125 (2003) 16081.
[34] J.S. Ovens, K.N. Truong, D.B. Leznoff, Dalton Trans. 41 (2012) 1345.
[35] E.S. Kryachko, J. Mol. Struct. 880 (2008) 114.
[36] A. Martı´nez, J. Phys. Chem. A 113 (2009) 1134.
[37] T.V. Baukova, L.G. Kuz'mina, N.A. Oleinikova, D.A. Lemenovskii, A.L. Blumenfel'd. J.
Organomet. Chem. 530 (1997) 27.
[38] A. Castiñeiras, N. Fernández-Hermida, R. Fernández-Rodríguez, I. García-Santos, Cryst.
Growth. Des. 12 (2012) 1432.
[39] L.-I. Rodríguez, T. Roth, J.L. Fillol, H. Wadepohl, L.H. Gade, Chem.-Eur. J. 18 (2012)
3721.
[40] M. Frik, J. Jiménez, I. Gracia, L.R. Falvello, S. Abi-Habib, K. Suriel, T.R. Muth, M. Contel,
Chem.-Eur. J. 18 (2012) 3659.
[41] M. Hejda, L. Dostál, R. Jambor, A. Růžička, R. Jirásko, J. Holeček, Eur. J. Inorg. Chem.
(2012) 2578.
[42] Y.-P. Zhou, M. Zhang, Y.-H. Li, Q.-R. Guan, F. Wang, Z.-J. Lin, C.-K. Lam, X.-L. Feng,
H.-Y. Chao, Inorg. Chem. 51 (2012) 5099.
[43] H. Nuss, M.Z. Jansen, Naturforsch. 61b (2006) 1205.
17

ACCEPTED MANUSCRIPT
[44] H. Nuss, M. Jansen, Angew. Chem. Int. Ed. 45 (2006) 4369.
[45] P.D.C. Dietzel, M. Jansen, Chem. Commun. (2001) 2208.
[46] H. Schmidbaur, H.G. Raubenheimer. L. Dobrzanska, Chem. Soc. Rev. 43 (2014) 345.
[47] K.J. Kilpin, R. Horvath, G.B. Jameson, S.G. Telfer, K.C. Gordon, J.D. Crowley,
Organometallics 29 (2010) 6186.
[48] G. Hogarth, M.M. Alvarez-Falcon, Inorg. Chim. Acta 358 (2005) 1386.
[49] C. Croix, A. Balland-Longeau, H. Allouchi, M. Giorgi, A. Duchene, J. Thibonnet, J.
Organomet. Chem. 690 (2005) 4835.
[50] V.W.-W. Yam, K.-L. Cheung, S.-K. Yip, N. Zhu, Photochem. Photobiol. Sci. 4 (2005) 149.
[51] L. Koskinen, S. Jääskeläinen, E. Kalenius, P. Hirva, M. Haukka, Cryst. Growth. Des. 14
(2014) 1989.
[52] A.K. Bar, S. Shanmugaraju, K.-W. Chi, P.S. Mukherjee, Dalton Trans. 40 (2011) 2257.
[53] S. Ghosh, R. Chakrabarty, P.S. Mukherjee, Inorg. Chem. 48 (2009) 549.
[54] A.K. Bar, B. Gole, S. Ghosh, P.S. Mukherjee, Dalton. Trans. (2009) 6701.
[55] C.-H. Tao, N. Zhu,. V. W.-W. Yam, Chem. Eur. J. 11 (2005) 1647.
[56] (27) (a) M. Kessinger, J. Michl. Excited States and Photochemistry of Organic Molecules
VCH New York 1995.
[57] M-H. Nguyen, C-Y. Wong, J. H. K. Yip. Organometallics (2013) 32 1620.
18

ACCEPTED MANUSCRIPT
[58] N. Agarwal, M. Patil M. Patil. RSC Adv. 5 (2015) 98447.
[59] Y-P. Ou, C. Jiang, D. Wu, J.Y. Xia, S. Jin, G.-A. Yu, S.H. Liu, Organometallics 30 (2011)
5763.
[60] 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.A.
Montgomery, Jr.; 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, D.J. Fox,. Gaussian 09, Revision D.01; Gaussian, Inc.: Wallingford, CT, 2009.
[61] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
[62] C. Lee, W. Yang, R. G. Parr, Phys. Rev. B: Condens. Matter. 37 (1988) 785.
[63] T.H. Dunning, Jr. P.J. Hay, Modern Theoretical Chemistry, Plenum, New York, 1976, vol.
3.
[6] R. Ditchfield, W J. J Hehre, A. Pople, J. Chem. Phys. 54 (1971) 724.
[65] V. Barone, M. Cossi, J. Phys. Chem. A 102 (1998) 1995.
[66] M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem. 24 (2003) 669.
19

ACCEPTED MANUSCRIPT
[67] M.T. Stone, H.L. Anderson. Chem. Commun. (2007) 2387.
[68] W. Fudickar, T. Linker. J. Am. Chem. Soc. 134 (2012) 15071.
[69] J. Kaleta, E. Kaletova,́ I. Císarova S.J. Teat, J. Michl. J. Org. Chem. 80 (2015) 10134.
[70] Y. Li, M.E. Köse, K.S. Schanze. J. Phys. Chem. B 117 (2013) 9025.
[71] Y. Sagara, S. Yamane, T. Mutai, K. Araki, T. Kato. Adv. Funct. Mater. 19 (2009) 1869.
[72] M. Pauvert, P. Laine, M. Jonas, O. Wiest. J. Org. Chem. 69 (2004) 543.
[73] J.-H. Lamm, J. Glatthor, J.-H. Weddeling, A. Mix, J. Chmiel, B. Neumann, H.-G. Stammler,
N.W. Mitzel, Org. Biomol. Chem. 12 (2014) 7355.
[74] G.M. Sheldrick, Acta Crystallogr. Sect. A A64 (2008) 112. Program for Crystal Structure
Solution and Refinement; University of Göettingen: Göettingen, Germany, 1997.
20

ACCEPTED MANUSCRIPT
List of figures and schemes.
Scheme 1. Synthetic outline for 1.
21

ACCEPTED MANUSCRIPT
Scheme 2. Synthetic outlines for 2 and 3.
22

ACCEPTED MANUSCRIPT
Fig. 1. Perspective view of 1. (Solvent molecules are omitted for clarity). Selected bond
distances (Å) and bond angles (deg): Au(1)–P(1) 2.281(3), Au(1)–C(1) 2.004(5), P(1)–Au(1)–
C(1) 175.1(2), Au(1)–C(1)–C(2) 173.7(4)
23

ACCEPTED MANUSCRIPT
Fig. 2. AuꢀꢀꢀH−C bonded supramolecular 2D network of 1 through tilted
a axis.
24

ACCEPTED MANUSCRIPT
Fig. 3. Perspective view of 2. Selected bond distances (Å) and bond angles (deg): Au(1)–P(1)
2.277(5), Au(1)–C(1) 2.03(3), P(1)–Au(1)–C(1) 176.8(6), Au(1)–C(1)–C(2) 172.4(17).
25

ACCEPTED MANUSCRIPT
Fig. 4. Perspective view of 3. distances (Å) and bond angles (deg): Au(1)–P(1) 2.271(7), Au(2)–
P(2) 2.282(6), Au(1)–C(1) 1.94(3), Au(2)–C(3) 1.94(3), C(1)–C(2) 1.21(3), C(3)–C(4) 1.23(3);
P(1)–Au(1)– C(1) 173.0(6), P(2)–Au(2)–C(3) 175.7(9), Au(1)–C(1)–C(2) 168.1(19), Au(2)–
C(3)–C(4) 169(2).
26

ACCEPTED MANUSCRIPT
Fig. 5. Wave like 1D polymeric chain of 2 showing CH-π and π-π interactions.
27

ACCEPTED MANUSCRIPT
Fig. 6. Intramolecular Au…HC interactions in 3.
28