Syntheses, Crystal Structure, and Photoluminescence Property of One Novel Compound Derived from Dicarboxylate and N-Donor Ligands

Article abstract of DOI:10.1080/15533174.2015.1031012

One novel compound constructed from aromatic acid and N-heterocyclic ligands has been synthesized by hydrothermal reaction: [Mn(ipm)(1,8-NDC)(H₂O)]₂ (1) [ipm = 5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol, 1,8-NDC =

Full text of DOI:10.1080/15533174.2015.1031012

Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry
ISSN: 1553-3174 (Print) 1553-3182 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt20
Syntheses, Crystal Structure, and
Photoluminescence Property of One Novel
Compound Derived From Dicarboxylate and N-
Donor Ligands
Li Yan & Mingzhe Sun
To cite this article: Li Yan & Mingzhe Sun (2016) Syntheses, Crystal Structure, and
Photoluminescence Property of One Novel Compound Derived From Dicarboxylate and
N-Donor Ligands, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal
Chemistry, 46:4, 556-560, DOI: 10.1080/15533174.2015.1031012
To link to this article: http://dx.doi.org/10.1080/15533174.2015.1031012
Published online: 18 Nov 2015.
Submit your article to this journal
Article views: 4
View related articles
View Crossmark data
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=lsrt20
Download by: [University of Nebraska, Lincoln]
Date: 25 November 2015, At: 22:46

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry (2016) 46, 556–560
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2015.1031012
Syntheses, Crystal Structure, and Photoluminescence Property
of One Novel Compound Derived From Dicarboxylate
and N-Donor Ligands
LI YAN1 and MINGZHE SUN2
1College of Chemistry, Jilin Normal University, Siping, P. R. China
2School of Food Production Technology, Changchun Vocational Institute of Technology, Changchun, P. R. China
Received 23 April 2013; accepted 11 June 2013
One novel compound constructed from aromatic acid and N-heterocyclic ligands has been synthesized by hydrothermal reaction:
[Mn(ipm)(1,8-NDC)(H2O)]2 (1) [ipm D 5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-2-methoxyphenol, 1,8-NDC D naphthalene-
1,8-dicarboxylic acid]. The title compound was obtained by controlling the ratio of the starting materials and a reaction temperature
at 170ꢀC and was characterized by elemental analysis, IR, single-crystal X-ray diffraction, and thermogravimetric analysis (TGA).
Single-crystal X-ray investigation reveals that compound 1 is zero dimensional (0D) structure, and the existence of hydrogen bonds
and p-p interactions lead the 0D to 1D chain framework. Hydrogen bonds interactions are powerful noncovalent intermolecular
interactions for directing supramolecular architectures. TGA shows three clear courses of weight loss, which corresponds to the
decomposition of different ligands. At room temperature, compound 1 exhibits emission at 535 nm upon excitation at 325 nm.
Fluorescent spectrum displays that compound 1 is potential luminescent material.
Keywords: crystal structure, noncovalent interactions, fluorescence, infrared spectrum
Introduction
supramolecular architectures.[8–12] Select suitable multidentate
ligands such as poly-carboxylate and N-heterocyclic ligands is a
Much of recent interest in the rapidly growing field of metal- successful approach to design and controlled synthesis of coordi-
organic frameworks (MOFs) coordination polymers derives nation polymers. Multicarboxylate ligands have been demon-
from the applied potential of these materials catalysis, porosity, strated as top-rank candidates, because of their versatile
sensors, magnetism, luminescence, molecular recognition, non- coordination modes and strong coordination ability, for the for-
linear optics and electrical conductivity.[1–7] In this regard, much mation of 1D, 2D, or 3D frameworks. However, naphthalene-
progress has been made on the design and synthesis of novel 1,8-dicarboxylic acid (1,8-NDC) is rarely reported, which inspir-
coordination frameworks and the relationships between their its our interest in it. In this study, we synthesized a novel N-het-
structures and properties. Therefore, systematic research on this erocyclic ligand: 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]
topic is still very necessary and important. However, rational phenanthroline (ipm) in view of the following characteristics: (a)
design and controllable preparation of metal–organic coordina- it possesses extended long-conjugated unsymmetrical aromatic
tion polymers still remains a long-term challenge for the chem- system to provide supramolecular interactions; (b) it has two
ists, and it is difficult to predict and control the final structure of nitrogen atoms, which is similar with 2,20-bipyridyl-like biden-
coordination compounds constructed by poly-carboxylate and tate chelating molecules; (c) it is a planar rigid bidentate chelat-
N-heterocyclic ligands. Generally, there are two different types ing ligand, which can provide supramolecular interactions such
of interactions: covalent bonds and noncovalent interactions, as aromatic stacking to construct intriguing structures; and (d) it
which can be used to construct varied supramolecular architec- possesses strong coordination ability.[13]
tures. To date, relatively less attention has been given to nonco-
For the past several years, we have worked on the synthe-
valent interactions, although, noncovalent interactions can be sis of the ipm similar ligands.[14–16] However, the investiga-
one of the most powerful force for instructing and directing the tion for this type of N-heterocyclic ligands is not enough. In
this paper, we design and synthesize one compound, namely:
[Mn(ipm)(1,8-NDC)(H2O)]2 1. Noncovalent intermolecular
interactions (coordination bonds, hydrogen bonds and p-p
interactions) play an important role in the architectures,
Corresponding author: Li Yan, College of Chemistry, Jilin Nor-
mal University, Siping, 136000, P. R. China. E-mail:
which favor construction of higher dimensional super-molec-
yanli820618@163.com
ular framework and reinforce the structural stability. The
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.
research shows that 1 is good luminescent material.

One Novel Compound
Experimental
Materials
557
Table 1. Crystal data and details of structure refinement parame-
ters for 1
Compound
1
The ligands ipm was prepared according to the description
in the literature procedures.[17] The metallic salt, 1,8-NDC,
and NaOH, were purchased commercially and used without
further purification.
Empirical formula
Formula weight
Crystal system
space group
C64H44Mn2N8O14
1258.95
Monoclinic
P-1
a (nm)
b (nm)
c (nm)
b (o)
Volume (nm3)
Z
0.78451(6)
1.48781(1)
2.29712(1)
90.7860(1)
2.6270(3)
2
Physical Measurements
The FT-IR spectrum was measured with KBr pellets in the
range of 4000–400 cm¡1 on a Perkin Elmer 240C spectrom-
eter. TGA was performed using a Perkin Elmer TG-7 ana-
lyzer at the rate of 10ꢀC/min rise of temperature in nitrogen
atmosphere. Crystal structures were determined on a Bruker
SMART APEX II CMN X-ray diffractometer. Carbon,
hydrogen and nitrogen elemental analyses were performed
with a PE-2400 elemental analyzer. Fluorescence spectra
were recorded on a FLSP 920 Edinburgh fluorescence
spectrometer.
Density (Mg/m3) (calcd.)
Absorption coefficient (mm¡1
F(000)
1.592
0.565
1292
0.43 £ 0.31 £ 0.29
0.90–25.99
14467
10170 [0.0169]
0.964
)
Crystal size (mm3)
Theta range
Reflections collected
Unique reflections [Rint
]
Goodness-of-fit on F2
Final R indices [I > 2s (I)]
R indices (all data)
R1 D 0.0411
wR2 D 0.1082
R1 D 0.0994
wR2 D 0.1353
0.720, –0.345
Syntheses
Ligand ipm: A mixture of 4-hydroxy-3-methoxybenzalde-
hyde, 1,10-phenanthroline-5,6-dione (0.525 g, 2.5 mmol),
ammonium acetate (3.88 g, 50 mmol) and glacial acetic
acid was refluxed for 4 h, then cooled to room temperature.
Yellow precipitate was obtained when addition of concen-
trated aqueous ammonia to neutralize, which was collected
and washed with water. The crude product dissolved in eth-
anol was purified by filtration on silica gel. The principal yel-
low band was obtained. Then evaporation of the solution
gave yellow products. Yield 0.57 g, 70%.
ꢀ
Largest difference peak and hole (e. A¡3
)
were refined isotropically. Experimental details for crystallo-
graphic data and structure refinement parameters for com-
pound 1 are listed in Table 1.
[Mn(ipm)(1,8-NDC)(H2O)]2 (1):
A mixture of ipm
(0.105 g, 0.3 mmol), MnSO4¢5H2O (0.051 g, 0.3 mmol),
1,8-NDC (0.130 g, 0.6 mmol) in distilled H2O (18 mL) was
stirred at room temperature and adjusted the pH value
to about 7.0 with NaOH. We put the cloudy solution into a
30-mL Teflon-lined stainless vessel at 170ꢀC for 72 h and
afterward cooled to room temperature at a rate of 5ꢀC/h.
The yellow crystals of compound 1 were obtained in 71%
yield based on Mn. C64H44Mn2N8O14: Anal. Calcd. C 61.05,
H 3.52, N 8.90%; Found: C 61.39, H 3.41, N 8.88%. IR
(KBr, cm¡1): 3119(s), 1620(vs), 1539(vs), 1394(vs), 1195(s),
1011(s), 886(s), 521(m), 487(m).
Results and Discussion
Structural Analysis of Compound 1
The molecular structure is shown in Figure 1, and the 1 D
chain structure is shown in Figure 2. Selected bond lengths
and bond angles are given in Table 2.
Single-crystal X-ray structural analysis reveals that the
asymmetric unit of compound 1 contains two Mn (II) atoms,
X-Ray Crystallography
Single-crystal X-ray diffraction data for compound 1 was col-
lected at 293(2) K with a Bruker SMART APEX II CMN
diffractometer equipped with a graphite-monochromatized
ꢀ
MoKa radiation (λ D 0.71073 A) at 293(2) K in the range of
0.90 ꢀ u ꢀ 25.99ꢀ for 1. Absorption corrections were applied
using multiscan technique and all the structures were solved
by direct methods and refined by full-matrix least-squares
based on F2 using the programs SHELXS-97[18] and
SHELXTL-97.[19] Non-hydrogen atoms were refined with
Fig. 1. The molecular structure of compound 1 (hydrogen atoms
anisotropic temperature parameters and all hydrogen atoms were omitted).

558
Yan and Sun
The 1,8-NDC ligands take bis-chelating and monodentate
bridging coordination modes to link two metal Mn(II)
atoms, and this lead to the formation of 0 D network.
There is 8-membered ring in the asymmetric unit of com-
pound 1, and the distance of adjacent Mn atoms is 4.5959
ꢀ
A. There are three kinds of H-bonds interactions in com-
pound 1: N–H. . .O, C–H. . .O, and O–H. . .O interactions.
The most interesting aspect of the structure in 1 concerns
ꢀ
the intermolecular of N–H. . .O [H(4A). . .O(2) D 1.98A, N
ꢀ
(4). . .O(2) D 2.798 A and N(4)–H(4A). . .O(2) D 177ꢀ]
interactions, which helps in the construction of the 1 D
chain structure (Figure 2). The N-heterocyclic ipm ligands
are attached to both sides of this chain regularly, and ipm
ligands on the same sides are parallel nearly. Moreover,
in compound 1, adjacent dimers are linked together
through p-p stackings (centroid-to-centroid distance of
Fig. 2. 1D chain structure by NꢁꢁH. . .O hydrogen bonds of com-
pound 1 (dotted lines represent hydrogen bonds).
ꢀ
ꢀ
two ipm ligands, two 1,8-NDC ligands, and two lattice H2O 3.661 A and face-to-face distance of 3.575 A) between
molecules. The Mn(II) atom is hexa-coordinated with two two 1,8-NDC ligands. Clearly, intermolecular p-p stack-
nitrogen atoms (N(1), N(2)) from one chelating ipm ligand ing and H-bonds interactions contribute to the stabiliza-
and four oxygen atoms ((O(2W) from one lattice water mole- tion of the structure of compound 1.
cule, O(1), O(2) from one bidentate 1,8-NDC, O(3) from
another distinct bridging monodentate 1,8-NDC ligand). For
the coordination environment of Mn(1), the Mn(1), O3, O1,
N1, N2 atoms define the basal plane, and the O2, O2W
IR Spectra
In compound 1, the two peaks at 1620 and 1539 cm¡1 corre-
atoms occupy the apical axial positions, forming a distorted
octahedral geometry. The N(O)–Mn–O(N) angles range are
spond to the antisymmetric stretching of carboxyl, the peak
at 1394 cm¡1 corresponds to the stretching of carboxyl. The
Dv (vas(COO¡)-vs(COO¡)) are 226 and 145 cm¡1, indicating
that the carboxyls adopt bidentate and monodentately coor-
dinated with Mn(II) atoms. The IR results are good agree-
ment with their solid structural features from the results of
their crystal structures.
from 86.32 to 166.16ꢀ. The bond distances of Mn–Ocarboxylic
ꢀ
ꢀ
D 2.100–2.259 A, Mn–Owater D 2.207–2.213 A, and those of
ꢀ
Mn–N bond distances fall in the 2.279–2.305 A range, which
are similar with the values reported.[20–25]
Each pair of adjacent Mn (II) atoms are bridged by
two 1,8-NDC ligands to form a dinuclear structure.[26,27]
ꢀ
Table 2. Selected bond lengths (A) and bond angles (ꢀ) for compound 1
Bond
Dist.
Bond
Dist.
Mn(1)-O(1)
Mn(1)-O(2)
Mn(1)-N(1)
Mn(2)-O(4)
Mn(2)-O(7)
Mn(2)-N(5)
Angle
2.100(4)
2.258(5)
2.290(5)
2.259(5)
2.111(4)
2.279(5)
(ꢀ)
Mn(1)-O(3)
Mn(1)-O(2W)
Mn(1)-N(2)
Mn(2)-O(5)
Mn(2)-O(1W)
Mn(2)-N(6)
Angle
2.117(4)
2.207(5)
2.305(5)
2.104(4)
2.213(5)
2.304(5)
(ꢀ)
O(1)-Mn(1)-O(3)
O(3)-Mn(1)-O(2W)
O(3)-Mn(1)-O(2)
O(1)-Mn(1)-N(1)
O(2W)-Mn(1)-N(1)
O(1)-Mn(1)-N(2)
O(2W)-Mn(1)-N(2)
N(1)-Mn(1)-N(2)
O(5)-Mn(2)-O(1W)
O(5)-Mn(2)-O(4)
O(1W)-Mn(2)-O(4)
O(7)-Mn(2)-N(5)
O(4)-Mn(2)-N(5)
O(7)-Mn(2)-N(6)
O(4)-Mn(2)-N(6)
107.29(17)
88.85(18)
95.79(19)
94.25(18)
88.32(19)
166.16(18)
93.6(2)
71.96(18)
87.83(18)
83.50(18)
171.28(15)
157.87(18)
90.52(19)
86.32(17)
95.30(19)
O(1)-Mn(1)-O(2W)
O(1)-Mn(1)-O(2)
O(2W)-Mn(1)-O(2)
O(3)-Mn(1)-N(1)
O(2)-Mn(1)-N(1)
O(3)-Mn(1)-N(2)
O(2)-Mn(1)-N(2)
O(5)-Mn(2)-O(7)
O(7)-Mn(2)-O(1W)
O(7)-Mn(2)-O(4)
O(5)-Mn(2)-N(5)
O(1W)-Mn(2)-N(5)
O(5)-Mn(2)-N(6)
O(1W)-Mn(2)-N(6)
N(5)-Mn(2)-N(6)
86.94(18)
83.28(18)
170.05(15)
158.09(18)
90.58(19)
86.55(17)
95.44(19)
107.89(17)
87.68(18)
95.87(19)
93.85(18)
89.11(19)
165.78(18)
92.87(19)
71.97(18)

One Novel Compound
559
(excitation at 325 nm) for ipm. Compound 1 exhibits one
broad emission band with the maximum intensity at 535 nm
upon excitation at 325 nm, which is red-shifted by 38 nm rel-
ative to the emission wavelength of free ligand ipm. It is
worth to mention that the heavy atom effect is quenching to
some extent, so the luminescent of compound 1 is weaker
than ipm ligand. The ipm ligand is rigid, and the rigidity is
favor of energy transfer and reduces the loss of energy
through a radiationless pathway. However, the effect of the
microenvironment between ligands and compounds on the
luminescence properties still needs further investigations. The
title compound may be good candidate for potential photolu-
minescence material because it is highly thermally stable and
insoluble in water and common organic solvents.
Conclusions
Fig. 3. TGA curves of compound 1.
In conclusion, we synthesized one novel compound by using
plane multifunctional ligands ipm, 1,8-NDC. It is noteworthy
that noncovalent interactions (H-bond and coordination
bonds) can be one of the most powerful forces for instructing
and directing the supramolecular architectures, as well as
reinforcing the structural stability of the title compound. TG
analysis reveals that the title compound is very stable and
worthy of further study as candidate of potential photolumi-
nescence material.
Thermal Properties
To examine the stability of compound 1, we examined the
TGA curves of crystalline samples in the flowing nitrogen
atmosphere at a heating rate of 10ꢀC/min (Figure 3). As
expected, in compound 1, the first weight loss corresponding
to the removal of lattice H2O is 2.90% (calcd. 2.68%) from
107 to 145ꢀC. The second weight loss of 31.80% from 145 to
438ꢀC corresponds to the loss of 1,8-NDC ligands (calcd.
32.22%). The last weight loss of 47.20% in the temperature
range of 438–564ꢀC can be ascribed to the release of ipm
ligands (calcd. 48.60%). The analysis results indicate that the
framework of compound 1 is very stable.
Funding
The authors thank the National Natural Science Foundation
of China (No. 20971019) and the Science Development Proj-
ect of Jilin Province of China (20130522071JH) for financial
support.
Photoluminescent Properties
Luminescence property is very important in photochemistry
and photophysics.[28,29] So in this study, we research the lumi-
nescence of compound 1, as well as the free ligand ipm
(Figure 4). The free ligand exhibits emission at 497 nm
Supplementary Material
CCDC 932169 contains the supplementary crystallographic
data for 1. These data can be obtained free of charge from
the Cambridge Crystallographic Data Centre via www.
cMnc.cam.ac.uk/data requestcif.
References
1. Batten, S. R.; Robson, R. Angew. Chem. Int. Ed. 1998, 37, 1460.
2. Wu, C. D.; Hu, A.; Zhang, L.; Lin, W. B. J. Am. Chem. Soc. 2005,
127, 8940.
3. Rowsell, J. L. C.; Yaghi, O. M. J. Am. Chem. Soc. 2006, 128, 1304.
4. Evans, O. R.; Lin, W. Acc. Chem. Res. 2002, 35, 511.
5. Zhang, J. P.; Lin, Y. Y.; Huang, X. C.; Chen, X. M. J. Am. Chem.
Soc. 2005, 127, 5495.
6. Moulton, B.; Zaworotko, M. J. Chem. Rev. 2001, 101, 1629.
7. Zheng, S. L.; Zhang, J. P.; Wong, W. T.; Chen, X. M. J. Am. Chem.
Soc. 2003, 125, 6882.
8. Yang, J.; Wu, B.; Zhuge, F.; Liang, J. J.; Jia, C. D.; Wang Y. Y,
Tang, N.; Yang, X. J.; Shi, Q. Z. Cryst. Growth Des. 2010, 10, 2331.
9. Liu, Q. X.; Zhao, X. J.; Wu, X. M.; Yin, L. N.; Guo, J. H.; Wang,
X. G.; Feng, J. C. Inorg. Chim. Acta 2008, 361, 2616.
Fig. 4. Luminescent spectrum of ligand ipm and compound 1 in
solid state at room temperature.

560
Yan and Sun
10. Li, G. N.; Xiong, J.; Liao, Y.; Sun, L.; Li, Y. Z.; Zuo, J. L. Polyhe- 20. Geng, W. Q.; Li, X. L.; Yin, J. H.; Zhou, H. P.; Wu, J. Y.; Tian, Y.
dron 2011, 30, 2473. P. Inorg. Chem. Comm. 2010, 13, 1285.
11. Hu, F.; Yin, X.; Mi, Y.; Zhang, S.; Luo, W.; Zhuang, Y. Inorg. 21. Yang, F.; Ren, Y.; Li, D.; Fu, F.; Qi, G.; Wang, Y. J. Mol. Struct.
Chem. Comm. 2010, 13, 33. 2008, 892, 283.
12. Zhang, S.; Wei, Q.; Xie, G.; Yang, Q.; Chen, S. Inorg. Chim. Acta 22. Zhang, J.; Li, B.; Wu, X.; Yang, H.; Zhou, W.; Meng, X.; Hou, H.
2012, 387, 52.
J. Mol. Struct. 2010, 984, 276.
13. Huang, Y. J.; Ni, L. J. Inorg. Organomet. Polym. 2011, 21, 97.
23. Zhang, Z.; Pi, M.; Wang, T.; Jin, C. M. J. Mol. Struct. 2011, 992, 111.
14. Yan, L.; Li, C. B.; Zhu, D. S.; Xu, L. J. Inorg. Organomet. Polym. 24. Hu, M.; Yang, X. G.; Zhang, Q.; Zhou, L. M.; Fang, S. M.; Liu, C.
2012, 22, 236. S. Z. Anorg. Allg. Chem. 2011, 637, 480.
15. Yan, L.; Li, C. B.; Zhu, D. S.; Xu, L. J. Inorg. Organomet. Polym. 25. Li, S. L.; Lan, Y. Q.; Ma, J. F.; Yang, J.; Wei, G. H.; Zhang, L. P.;
2012, 22, 395.
Su, Z. M. Cryst. Growth Des. 2008, 8, 680.
16. Yan, L.; Li, C. B.; Zhu, D. S.; Xu, L. J. Mol. Struct. 2012, 1002, 172.
17. Steck, E. A.; Day, A. R. J. Am. Chem. Soc. 1943, 65, 452.
18. Sheldrick, G. M. SHELXS 97, Program for the Solution of Crystal
26. Nie, F. M.; Li, M.; Li, G. X. J. Mol. Struct. 2010, 977, 45.
27. Yang, F.; Ren, Y. X.; Li, D. S.; Fu, F.; Qi, G. C.; Wang, Y. Y. J.
Mol. Struct. 2008, 892, 283.
€
Structure; University of Gottingen, Germany, 1997
28. Chen, C. H.; Shi, J. M. Coord. Chem. Rev. 1998, 171, 165.
19. Sheldrick, G. M. SHELXS 97, Program for the Refinement of Crys- 29. Mizukami, S.; Houjou, H.; Sugaya, K.; Koyama, E.; Tokuhisa, H.;
€
tal Structure; University of Gottingen, Germany, 1997.
Sasaki, T.; Kanesato, M. Chem. Mater. 2005, 17, 51.