Construction of HgII complexes containing chelating 2,2′-dipyridylamine ligands: Anion effect, photoluminescence and catalytic activities

Article abstract of DOI:10.1016/j.inoche.2011.10.026

Five new structures of Hg^II complexes containing Hdpa ligands have been determined. With halides, tetrahedral Hg^II is constructed by a Hdpa and two chlorides or bromides, and strong hydrogen bonds between amine hydrogen atoms and halide atoms provide dimeric compounds. With benzoates, distorted octahedral Hg^II is constructed by a Hdpa and two chelating benzoate ligands, and hydrogen bonding and π-π interactions provide a polymeric compound. With nitrates or perchlorates, two dpa ligands bridge two HgII ions, and counter-anions axially coordinate to Hg^II ions to form a polymeric compounds. In addition, all five Hg^II complexes showed the intense emissions at room temperature, which are red-shifted compared to the corresponding ligand. Moreover, 3 and 4 have shown efficient catalytic transesterification recation, while 1, 2 and 5 has displayed a very slow conversion.

Full text of DOI:10.1016/j.inoche.2011.10.026

Inorganic Chemistry Communications 15 (2012) 212–215
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Construction of HgII complexes containing chelating 2,2′-dipyridylamine ligands:
Anion effect, photoluminescence and catalytic activities
Ju Hoon Lee a,1, Hyun Min Park a,1, Seung Pyo Jang a,1, Geun Hee Eom a,1, Jeong Mi Bae a,1, Cheal Kim a,
⁎
,
b,2
b,⁎⁎
Youngmee Kim
, Sung-Jin Kim
a
Department of Fine Chemistry, Seoul National University of Science & Technology, Seoul 139-743, Republic of Korea
Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Republic of Korea
b
a r t i c l e i n f o
a b s t r a c t
Five new structures of HgII complexes containing Hdpa ligands have been determined. With halides, tetrahe-
dral HgII is constructed by a Hdpa and two chlorides or bromides, and strong hydrogen bonds between amine
hydrogen atoms and halide atoms provide dimeric compounds. With benzoates, distorted octahedral HgII is
constructed by a Hdpa and two chelating benzoate ligands, and hydrogen bonding and π–π interactions pro-
vide a polymeric compound. With nitrates or perchlorates, two dpa ligands bridge two HgII ions, and
counter-anions axially coordinate to HgII ions to form a polymeric compounds. In addition, all five HgII com-
plexes showed the intense emissions at room temperature, which are red-shifted compared to the corre-
sponding ligand. Moreover, 3 and 4 have shown efficient catalytic transesterification recation, while 1, 2
and 5 has displayed a very slow conversion.
Article history:
Received 19 July 2011
Accepted 17 October 2011
Available online 25 October 2011
Keywords:
Mercury(II) nitrate
2,2′-dipyridylamine
Anion effects
Photoluminescence
Transesterification
© 2011 Elsevier B.V. All rights reserved.
Self-assembly process for the construction of coordination com-
plexes and polymers [1–6] has been affected by the hydrogen bonds
[7–13], π–π stacking [14], and anions [15–19] as well as ligand struc-
tures [20] and metal ions [21,22]. Among them, the anions could play
very important roles on the self-assembled construction of coordination
polymers. In recent years, we have shown that 2,2′-dipyridylamine
(Hdpa) as a chelating ligand mostly formed mono- or dinuclear ZnII
transesterification reactions under mild reaction conditions and HgII–
Hdpa complexes with photoluminescence properties, we employed
mercury salts with different counter-anions (halides, benzoate, nitrate
and perchlorate,).
Five mercury salts HgCl2, HgBr2, Hg(O2CC6H5)2, Hg(NO3)2, and
Hg(ClO4)2 were reacted with 2,2′-dipyridylamine (Hdpa) to produce
[Hg(Hdpa)X2]2 (X=Cl (1) and Br (2)), [(Hg(Hdpa)(O2CC6H5)2] (3),
[Hg2(dpa)2(NO3)2] (4), and [Hg2(dpa)2]n·(ClO4)2n (5). Colorless crys-
tals were obtained from the direct diffusion technique with two sol-
vent systems, and their structures were determined by X-ray
crystallography. Various structures of HgII–Hdpa system according
to counter-anions are shown in Scheme 1.
Hdpa has been used as a chelating ligand to mostly form mononu-
clear ZnII complexes [23–27], and then these ZnII complexes could be
used as building blocks for one-, two-, or three-dimensional structures
through weak hydrogen bonding and π–π interactions. For the corre-
sponding CdII complexes containing chelating Hdpa ligands with vari-
ous anions, different structures have been obtained according to
counter-anions [28, 29]. These results indicated that both inter-
molecular hydrogen bonds and π–π interactions as well as anion effects
also play very important roles in the construction of crystal structures in
both ZnII and CdII systems. To complete investigation for anion effects
on construction of Group 10 metal compounds containing Hdpa ligands,
the corresponding HgII compounds with various anions (chloride,
bromide, nitrate, benzoate, and perchlorate) have been adopted in
this system. Different structures have been obtained according to
counter-anions for all Group 10 metal ions as shown in Table 1.
and CdII complexes according to anions (anions used; halides, NO3−
,
−O2CC6H5, ClO4−) [23–29], and then these ZnII and CdII complexes
could be used as building blocks for the three-dimensional structures
through weak hydrogen bonding and π–π interactions. In addition,
many of all these complexes catalyzed efficiently the transesterification
of a variety of esters with methanol, and showed the luminescent
properties.
As a part of our continued interests in the syntheses, structures,
and reactivities of coordination complexes with chelating Hdpa
ligands, and with the aim to fully understand the anion and metal
effects on construction of a variety of Group 10 metal complexes
containing chelating Hdpa ligands, to compare the structural diversi-
ty of ZnII- and CdII–Hdpa complex systems with a HgII–Hdpa com-
plex system, and to find efficient catalysts to mediate catalytic
⁎
Corresponding author. Tel.: +82 2 970 6693; fax: +82 2 973 9149.
⁎⁎ Corresponding author. Tel.: +82 2 3277 3589; fax: +82 2 3277 3419.
E-mail addresses: chealkim@snut.ac.kr (C. Kim), ymeekim@ewha.ac.kr (Y. Kim).
1
Tel.: +82 2 970 6693; fax: +82 2 973 9149.
Tel.: +82 2 3277 3589; fax: +82 2 3277 3419.
2
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.10.026

J.H. Lee et al. / Inorganic Chemistry Communications 15 (2012) 212–215
213
Scheme 1. Various structures of HgII complexes.
Chloride and bromide could be used as simple coordinating ligands
in HgII–Hdpa system as ZnII–Hdpa system while they were used for
CdII ions as both simple coordinating and bridging ligands. The strong
hydrogen bonds between amine hydrogen atoms and halide atoms
provide dimeric compounds in HgII–Hdpa system (Scheme 1 and
Fig. S1). For halide ligands, ZnII and HgII prefer tetrahedral geometry,
but the coordination on CdII ion changes from octahedral to trigonal
bipyramidal and tetrahedral. Benzoate anions were used as chelating
ligands in Group 10 metal ions with very similar structures. Inter-
molecular hydrogen bond interactions and π–π interactions between
pyridyl rings provide polymeric structures for all Group 10 metal
ions (Scheme 1 and Fig. S2). Nitrate anions could be used as the simple
O-donor coordinating ligands for HgII ions as CdII ions while they were
used as chelating ligands for ZnII ions. For HgII ions, two dpa ligands
(deprotonated) bridge two HgII ions to form a dinuclear complex
with axially coordinated nitrate ligands (Scheme 1 and Fig. S3). The
weak bonds between HgII ions and nitrate oxygen atoms provide
a polymeric structure. For ClO4− anions, HgII ions also provide a dpa-
bridged dinuclear complex with axially coordinated perchlorate
ligands while perchlorate ions act as non-coordinating ligands for
Table 1
Different structures for Group 10 metal ions according to the counter-anions.

214
J.H. Lee et al. / Inorganic Chemistry Communications 15 (2012) 212–215
ZnII–Hdpa and CdII–Hdpa systems. The weak bonds between HgII ions
and perchlorate oxygen atoms also provide a polymeric structure.
These results confirm that both inter-molecular hydrogen bonds and
π–π interactions as well as anion effects also play very important
roles in the construction of crystal structures in HgII–Hdpa system,
and these results also indicate that metal ions play a very important
role for crystal structures in all Group 10 metal ion systems.
homogeneous conditions (Eq. (1); see the Supporting Information
for details).
ð1Þ
Since luminescent compounds are of great current interest due
to their various applications in chemical sensors, photochemistry,
and electroluminescent display [30] and since complexes containing
Group 10 metal ions such as cadmium and zinc exhibit photolumines-
cent properties [31,32], the luminescent properties of compounds 1–5
have been investigated. The photoluminescent spectra of compounds
1–5 and Hdpa ligand have been measured in the solid state at
room temperature. Emissions of compounds 1–5 were observed at
421 nm (λex =330 nm) for 1, 419 nm (λex =330 nm) for 2, 458 nm
(λex =366 nm) for 3, 443 nm (λex =368 nm) for 4, and 446 nm
(λex =356 nm) for 5, respectively, while that of Hdpa was observed
at 372 nm (λex =330 nm) under the same experimental conditions
(Fig. 1). The emission bands of complexes 1–5 are red-shifted com-
pared to the corresponding ligand, which indicates that the emission
peaks of 1–5 may be attributed to the metal-to-ligand charge transfer
(MLCT) and/or ligand-to-metal charge transfer (LMCT). In addition,
complexes 3–5 show more red-shifted emissions than complexes 1
and 2, assuming that a type of anions, halide group versus non-
halide group, results in the difference. Moreover, more intense emis-
sions of complexes 4 and 5 compared with those of other complexes
at room temperature might be attributed to effective increase of the ri-
gidity of the complex and reduces the loss of energy by radiationless
decay. Furthermore, the intense emissions of 1, 2, 3, 4, and 5 at room
temperature suggest that they may be a good candidate for a potential
hybrid inorganic–organic photoactive material [32].
This reaction produced quantitatively the corresponding product
methyl acetate within 0.92–20 days, while a control reaction carried
out in absence of the complexes showed trace amounts of the conver-
sion of the ester to the product in the same time period. 3 and 4 have
shown efficient catalytic reactivities (4 and 0.92 days), while 1, 2 and
5 have displayed a very slow conversion (12, 18, and 20 days). Impor-
tantly, this result is the first example that the Hg complexes contain-
ing bipyridyl ligands catalyze the transesterification reactions, to our
best knowledge [33–38]. In addition, the catalytic reactivity of 4 is
comparable to those of Cd catalysts which are known as the catalysts
for the transesterification reactions [29, 37, 38].
It has been proposed that the mechanism of metal ion catalyzed
transesterification probably involves electrophilic activation of the
carbon center of the carbonyl moiety by binding of the metal to the
carbonyl oxygen. Therefore, Lewis acidity of the metal center may
be important in catalytic transesterification. Based on this proposal,
a possible transesterification mechanism with the most efficient
catalyst 4 having a labile ligand NO3− can be proposed. The substrate
phenyl acetate substitutes the anion (NO3−) to give the adduct Hg2
(dpa)2(Sub). Then, the nucleophile methanol would attack the carbon
atom of carbonyl moiety of the adduct to produce the product methyl
acetate. At present, it is not clear why complex 5 having the labile
ligand ClO4− showed much worse reactivity than complex 4. Detailed
mechanistic studies are currently under investigation.
In summary, we have shown five new structures of HgII complexes
containing Hdpa ligands to complete anion effects on Group 10 metal
compounds. With halides, tetrahedral HgII is constructed by a Hdpa
and two chlorides or bromides, and strong hydrogen bonds between
amine hydrogen atoms and halide atoms provide dimeric compounds.
With benzoates, distorted octahedral HgII is constructed by a Hdpa
and two chelating benzoate ligands, and hydrogen bonding and π–π
interactions provide a polymeric compound. With nitrates and perchlo-
rates, two dpa ligands bridge two HgII ions, and counter-anions axially
coordinate to HgII ions to form a polymeric compounds. These results
confirm that both anion effects and metal effects play very important
roles on construction of crystal structures for Group 10 metal-Hdpa
compounds. Moreover, all five HgII complexes showed the intense
emissions at room temperature, which could be used as a good candi-
date for a potential hybrid inorganic–organic photoactive material.
Furthermore, 3 and 4 have shown efficient catalytic transesterification
reactions and these results are the first example that the HgII complexes
containing bipyridyl ligands catalyze the transesterification reactions.
As part of our efforts to develop transesterification catalysts,
we have previously reported that Zn(Hdpa)X2 (X=Cl−, Br−, I−
,
−O2CC6H5, NO3−, and SO42−) complexes could carry out the catalytic
transesterification of a range of esters with methanol at room tempera-
ture under the mild conditions [26,27]. Moreover, we have recently
shown that [Cd(Hdpa)1–3]Z2 (Z=Cl−, Br−, I− −O2CC6H5, NO3−, and
,
ClO4−) could also catalyzed the transesterification reactions of a series
of esters in spite of being well known as an inert metal [29]. In order
to compare the reactivity of the complexes containing Zn, Cd, and
Hg ions, therefore, we have examined the transesterification reaction
with the compounds 1–5. Thus, the compounds 1–5 were treated
with phenyl acetate and methanol at 50 °C under the neutral
Notes:
333.9 mg (0.125 mmol) of HgCl2 were dissolved in 1 mL methylene chloride and
42.8 mg (0.25 mmol) of Hdpa ligand were dissolved in 1 mL methanol. Then, these
two solutions were mixed, stirred for 3 h at room temperature and carefully layered
by 6 mL hexane. Suitable crystals of compound 1 for X-ray analysis were obtained in
2 days. The yield was 19.5 mg (35.2%) for compound 1. 1H NMR (DMSO, 400 MHz):
δ 9.70 (s, 1H, NH), δ 8.21 (m, 2H, pyridyl-H), δ 7.68 (m, 4H, pyridyl-H) and δ 6.88
(m, 2H, pyridyl-H). IR (KBr): ν(cm−1)=3314(m), 3212(m), 3148(w), 3030(w),
1635(s), 1582(s), 1529(s), 1475(s), 1428(s), 1378(w), 1227(s), 1159(s), 1059(w),
1007(m), 909(w), 828(w), 769(s), 641(w), 520(w). Anal. Calcd. for C10H9Cl2HgN3
(442.69), 1: C, 27.13; H, 2.26; N, 9.49. Found: C, 27.47; H, 2.21; N, 9.55%. 45.1 mg
(0.125 mmol) of HgBr2 were dissolved in 4 mL ethanol and carefully layered by 4 mL
methylene chloride of Hdpa ligand (42.8 mg, 0.25 mmol). Suitable crystals of com-
pound 2 for X-ray analysis were obtained in a few days. The yield was 54.9 mg
(82.6%) for compound 2. 1H NMR (DMSO, 400 MHz): δ 9.73 (s, 1H, NH), δ 8.21 (m, 2H,
pyridyl-H), δ 7.68 (m, 4H, pyridyl-H) and δ 6.89 (m, 2H, pyridyl-H). IR (KBr): ν(cm−1)=
3310(m), 3211(w), 1632(s), 1582(s), 1527(m), 1474(s), 1418(m), 1376(w), 1317(w),
1228(m), 1159(m), 1007(w), 908(w), 769(s). Anal. Calcd. for C10H9Br2HgN3 (531.61),
Fig. 1. Emission spectra of complexes 1–5 and ligand (Hdpa) at room temperature.

J.H. Lee et al. / Inorganic Chemistry Communications 15 (2012) 212–215
215
2: C, 22.59; H, 1.71; N, 7.91. Found: C, 22.83; H, 2.01; N, 8.13%. 49.9 mg (0.125 mmol) of Hg
(ben)2·H2O were dissolved in 1 mL methylene chloride and 42.8 mg (0.25 mmol) of Hdpa
ligand were dissolved in 1 mL methanol. Then, these two solutions were mixed, stirred for
3 h at room temperature and carefully layered by 6 mL hexane. Suitable crystals of com-
pound 3 for X-ray analysis were obtained in a week. The yield was 32.3 mg (42.1%) for
compound 3. 1H NMR (DMSO, 400 MHz): δ 8.20 (d, 2H, pyridyl-H), δ 7.96 (m, 4H,
data can be obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-
336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.inoche.2011.10.026.
pyridyl-H and benzoate-H),
δ 7.70 (m, 4H, NH and benzoate-H), δ 7.56 (m, 2H,
benzoate-H), δ 7.47 (m, 5H, pyridyl-H and benzoate-H) and δ 6.88 (t, 2H, pyridyl-H). IR
(KBr): ν(cm−1)=3321(w), 3209(w), 3076(w), 1649(m), 1598(s), 1554(s), 1536(s),
1479(s), 1376(s), 1232(m), 1163(m), 1071(w), 909(w), 851(w), 772(s), 728(s), 681(m),
518(w). Anal. Calcd. for C24H19HgN3O4 (614.01), 3: C, 47.29; H, 3.13; N, 6.85. Found: C,
46.85; H, 3.10; N, 6.91%. 43.7 mg (0.125 mmol) of Hg(NO3)2·H2O were dissolved in 1 mL
methylene chloride and 42.8 mg (0.25 mmol) of Hdpa ligand were dissolved in 1 mL
methanol. Then, these two solutions were mixed, stirred for 3 h at room temperature,
and left on a table. Suitable crystals of compound 4 for X-ray analysis were obtained in a
few hours. The yield was 51.9 mg (41.9%) for compound 4. 1H NMR (DMSO, 400 MHz): δ
8.12 (d, 4H, pyridyl-H), δ 7.86 (t, 4H, pyridyl-H), δ 7.35 (d, 4H, pyridyl-H) and δ 6.99 (m,
6H, NH and pyridyl-H). IR (KBr): ν(cm−1)=3080(w), 1603(m), 1480(s), 1441(s), 1385
(s), 1310(m), 1158(m), 1023(w), 913(w), 766(m), 529(w). Anal. Calcd. for C20H16Hg2N8-
O6 (865.59), 4: C, 27.75; H, 1.87; N, 12.95. Found: C, 28.03; H, 1.54; N, 12.76%. 49.9 mg
(0.125 mmol) of Hg(ClO4)2·H2O and 42.8 mg (0.25 mmol) of Hdpa ligand were stirred
in 2 mL methanol for 6 h at room temperature and carefully layered by 6 mL diethyl ether.
Suitable crystals of compound 5 for X-ray analysis were obtained in a month. The yield was
58.5 mg (63.1%) for compound 5. 1H NMR (DMSO, 400 MHz): δ 8.30 (d, 2H, pyridyl-H), δ
8.12 (d, 2H, pyridyl-H), δ 7.86 (m, 4H, pyridyl-H), δ 7.35 (m, 4H, pyridyl-H), δ 7.15 (m,
2H, pyridyl-H) and δ 6.99 (t, 2H, pyridyl-H). IR (KBr): ν(cm−1)=3440(w), 3210(w),
1641(w), 1604(m), 1582(w), 1527(w), 1479(s), 1440(s), 1316(w), 1232(w), 1121(s),
1094(s), 1047(m), 1006(w), 770(s), 632(s). Anal. Calcd. for C20H16Cl2Hg2N6O8 (940.47),
5: C, 25.54; H, 1.72; N, 9.00. Found: C, 25.61; H, 1.85; N, 8.91%.
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4Crystal data for1: C10H9Cl2HgN3, M=442.69, P-1, a=8.0180(16) Å, b=8.6100(17) Å,
c=9.6040(19) Å, α=110.63(3)°, β=99.03(3)°, γ=97.03(3)°,V=601.4(2) Å3, Z=2,
μ(Mo Kα)=13.215 mm−1, 3314 reflections measured, 2307 unique (Rint=0.0425) which
were used in all calculations, final R=0.0649 (Rw=0.1680) with reflections having inten-
sities greater than 2σ, GOF(F2)=1.017. Crystal data for 2: C10H9Br2HgN3, M=531.61, P-1,
a=8.1913(16) Å, b=8.8417(16) Å, c=9.9433(18) Å, α=112.875(3)°, β=97.817(4)°,
γ=97.411(3)°, V=644.2(2) Å3, Z=4, μ(Mo Kα)=18.126 mm−1, 3594 reflections mea-
sured, 2457 unique (Rint=0.0198) which were used in all calculations, final R=0.0340
(Rw=0.0812) with reflections having intensities greater than 2σ, GOF(F2)=1.001. Crystal
data for 3: C24H19HgN3O4, M=614.01, P 21/n, a=7.542(7) Å, b=16.549(14) Å, c=17.868
(15) Å, β=99.719(14)°, V=2198(3) Å3, Z=4, μ(Mo Kα)=7.039 mm−1, 11,014 reflec-
tions measured, 4220 unique (Rint=0.0898) which were used in all calculations, final
R=0.0507 (Rw=0.1208) with reflections having intensities greater than 2σ, GOF(F2)=
1.038. Crystal data for 4: C20H16Hg2N8O6, M=865.59, P 21/n, a=11.6447(13) Å, b=
13.2745(15) Å, c=15.5457(17) Å, β=98.092(2)°, V=3194(6) Å3, Z=4, μ(Mo Kα)=
12.945 mm−1, 12,739 reflections measured, 4615 unique (Rint=0.0391) which were used
in all calculations, final R=0.0358 (Rw=0.0876) with reflections having intensities
greater than 2σ, GOF(F2)=1.057. Crystal data for 5: C20H16Cl2Hg2N6O8, M=940.47, P 21/n,
a=11.7950(19) Å, b=12.573(2) Å, c=16.913(3) Å, β=104.809(3)°, V=2424.8(7) Å3,
Z=4, μ(Mo Kα)=12.929 mm−1, 13,043 reflections measured, 4736 unique (Rint =0.0530)
which were used in all calculations, final R=0.0363 (Rw=0.0731) with reflections having
intensities greater than 2σ, GOF(F2)=1.049. Structural information was deposited at the
Cambridge Crystallographic Data Center. CCDC 827034 for 1, 827033 for 2, 827031 for 3,
827032 for 4, and 827035 for 5.
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Financial support from Korean Science & Engineering Foundation
(2009–0074066), Converging Research Center Program through the
National Research Foundation of Korea (NRF) funded by the Ministry
of Education, Science and Technology (2009–0082832), and SRC pro-
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Appendix A. Supplementary material
CCDC 827034 for 1, 827033 for 2, 827032 for 3, 827031 for 4, and
827035 for 5 contains the supplementary crystallographic data. These