[Article] www.whxb.pku.edu.cn

物理化学学报(Wuli Huaxue Xuebao)

Acta Phys. ⁃Chim. Sin. 2012, 28 (12), 2783-2789December

Received: July 25, 2012; Revised: October 11, 2012; Published on Web: October 12, 2012.∗Corresponding authors. WEI Qing, Email: weiqq@126.com. CHEN San-Ping, Email: sanpingchen@126.com; Tel: +86-29-88302604.

The project was supported by the National Natural Science Foundation of China (21173168, 21073142, 21127004) and Science Research Projects of

Educational Department of Shaanxi Province, China (2010JK882, 2010JQ2007, 11JS110, 11JK0578).

国家自然科学基金(21173168, 21073142, 21127004)和陕西省教育厅科研基金(2010JK882, 2010JQ2007, 11JS110, 11JK0578)资助项目

Ⓒ Editorial office of Acta Physico⁃Chimica Sinica

doi: 10.3866/PKU.WHXB201210122

基于1H-苯并咪唑-2-羧酸的三个镧系超分子化合物的

结构、热分解动力学和荧光性质

段林强 1 乔成芳 1,2 魏 青 1,* 夏正强 1 陈三平 1,*

张国春 2 周春生 2 高胜利 1,2

(1西北大学化学与材料科学学院, 合成与天然功能分子化学教育部重点实验室, 西安 710069;2商洛学院化学与化学工程系, 陕西省尾矿资源综合利用重点实验室, 陕西商洛 726000)

摘要: 在水热条件下合成了三个镧系超分子化合物[Ln(HBIC)3]n [Ln=Sm (1), Ho (2), Yb (3); H2BIC=1H-苯并

咪唑-2-羧酸], 其中化合物1、2呈单晶态, 化合物3则为粉末样品; 借助单晶X射线衍射(XRD)、粉末衍射、元素

分析、红外(IR)光谱、热分析等手段对化合物进行了表征. 结构分析表明, 1-3为同构化合物, 都呈现二维的平面

结构, 其中每一个镧系金属中心与来自五个HBIC-配体的三个氮原子和五个氧原子以两种新的配位模式配位形

成一个轻微扭曲的双帽三棱柱几何构型, 相邻的二维(2D)平面进一步通过强的氢键作用形成了一个三维(3D)

的超分子结构. 热重分析结果表明, 化合物1-3在360 °C前均保持稳定, 呈现出良好的热稳定性. 基于Kissinger

和Ozawa-Doyle两种方法, 通过差示扫描量热(DSC)技术研究得到了化合物1热分解的动力学参数(指前因子

AK=1.286×108 s-1; 活化能EK=199.3 kJ·mol-1, EO=205.2 kJ·mol-1). 另外, 也研究了室温下化合物1和3的固态

发光性能, 结果表明, 化合物1和3分别在可见光区和近红外光区呈现出相应镧系金属离子的特征发射.

关键词: 镧系配合物; 1H-苯并咪唑-2-羧酸; 结构分析; 发光; 热分析动力学

中图分类号: O641

Structures, Thermodecomposition Kinetics and LuminescenceProperties of Three Lanthanide-Based Supramolecular Compounds

with 1H-Benzimidazole-2-carboxylic Acid

DUAN Lin-Qiang1 QIAO Cheng-Fang1,2 WEI Qing1,* XIA Zheng-Qiang1

CHEN San-Ping1,* ZHANG Guo-Chun2 ZHOU Chun-Sheng2 GAO Sheng-Li1,2

(1Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and

Materials Science, Northwest University, Xiʹan 710069, P. R. China; 2Department of Chemistry and Chemical

Engineering, Shaanxi Key Laboratory of Comprehensive Utilization of Tailing Resources,

Shangluo University, Shangluo 726000, Shaanxi Province, P. R. China)

Abstract: Three lanthanide-based supramolecular compounds, [Ln(HBIC)3]n (Ln=Sm (1), Ho (2), Yb (3);

H2BIC=1H-benzimidazole-2-carboxylic acid), were hydrothermally synthesized and structurally

characterized by X-ray single crystal diffraction (compounds 1 and 2), powder X-ray diffraction (XRD)

(compound 3), elemental analysis, infrared (IR) spectroscopy, and thermal analysis. Structural analyses

reveal that compounds 1-3 are isomorphous and display a two-dimensional (2D) plane, in which each

lanthanide center is coordinated by three N and five O atoms from five flexible HBIC- ligands with two kinds

of new coordination modes, giving rise to a slightly distorted two-capped triangle prism geometry. The 2D

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Acta Phys. ⁃Chim. Sin. 2012 Vol.28

square networks are further assembled into a three-dimensional (3D) supramolecular framework through

strong hydrogen-bonding interactions. Thermogravimetric analyses (TG) indicate that compounds 1-3

exhibit good thermostability and could be stable up to 360 °C. By means of differential scanning calorimetry

(DSC) techniques, the thermoanalysis kinetics parameters of the thermodecomposition of compound 1

were calculated by the Kissingerʹs and Ozawa-Doyleʹs methods; the pre-exponential factor AK was 1.286×

108 s-1 and the apparent activation energy EK and EO were determined to be 199.3 and 205.2 kJ·mol-1,

respectively. In addition, the luminescent properties of compounds 1 and 3 were also studied at room

temperature in the solid state. The results reveal that compounds 1 and 3 exhibit characteristic emission

bands of the corresponding lanthanide ions in the visible and near-infrared regions, respectively.

Key Words: Lanthanide coordination compound; 1H-Benzimidazole-2-carboxylic acid;

Structure analysis; Luminescence; Thermoanalysis kinetics

1 IntroductionIn recent years, the self-assembly of metal-organic frame-

works (MOFs) has been attracting more and more attention for

their fascinating architectures and potential applications as new

materials in ion exchange, magnetism, gas absorption, cataly-

sis, and luminescence.1-6 Particularly for the optical applica-

tions, extensive efforts have been devoted to the study of lan-

thanide-based MOFs (LnOFs), because the narrow f→f transi-

tions derived from 4f electrons of lanthanide ions could lead to

interesting and excellent luminescence emissions in visible or

near-infrared regions.7-10 Up to now, numerous one-dimension-

al (1D), two-dimensional (2D), and three-dimensional (3D) lan-

thanide compounds have been synthesized with appropriate

bridging organic ligands, and many of them exhibited extraor-

dinary luminescence and intriguing network topologies due to

the high coordination number, flexible coordination environ-

ments, and large radii of lanthanide ions.11-18 It can be conclud-

ed from the fruitful reports of LnOFs that the polytopic organic

ligands containing O- or N-donors are the preferred choice for

preparation of LnOFs.

Based on the consideration above, we focused on a flexible

heterocyclic ligand, 1H-benzimidazole-2-carboxylic acid

(H2BIC), which consists of benzimidazole ring bearing carbox-

ylate group (Scheme 1). Related reports indicated that H2BIC

was not only a reaction medium in synthesis but also a poten-

tial multifunctional organic linker for construction of

MOFs.19-22 Actually, H2BIC has many remarkable features. It

contains two carboxyl O atoms and two imidazole N atoms,

which can provide many coordination fashions, from terminal

monodentate coordination or N,O-bidentate-chelating to chelat-

ing-bridging or bi(chelating-bridging) modes, giving rise to

various LnOFs with charming architectures and functions. In

addition, the rigid benzimidazole ring is beneficial for the sta-

bility of the framework, and the carboxylate group could fur-

ther strengthen the conjugated systems when coordinating with

lanthanide ions, resulting in better sensitization for lanthanide

luminescence.

Hence, in this contribution, the multidentate H2BIC ligand

was used to construct new LnOFs [Ln=Sm (1), Ho (2), Yb (3)]

under hydrothermal conditions. In order to evaluate the ther-

mal effect on the target structures, thermogravimetry (TG) anal-

yses and thermonalysis kinetics for compound 1 were per-

formed. Additionally, the luminescent properties of compounds

1 and 3 were investigated.

2 Experimental2.1 Materials and methods

All of the reagents were purchased and used without further

purification. 1H-benzimidazole-2-carboxylic acid (97%) was

purchased from Xiʹan Chemblossom Pharmaceutical Technolo-

gy Co., Ltd., SmCl3·6H2O (99.9%), HoCl3·6H2O (99.9%),

YbCl3·6H2O (99.9%), and NaOH (97%) were purchased from

Sigma-Aldrich. Elemental analyses (C, H, N) were performed

on a Perkin-Elmer III elemental analyzer (USA). Infrared (IR)

spectra were recorded with a Tensor 27 spectrometer (Bruker

Optics, Ettlingen, Germany) in the range of 4000-400 cm-1 us-

ing powdered samples on a KBr pellets. Powder X-ray diffrac-

tion (PXRD) patterns were recorded on a Bruker D8 Advance

diffractometer (Germany). Thermogravimetric measurements

were performed with a Netzsch STA 449C apparatus (Germa-

ny) under air atmosphere from 20 to 1000 °C. Differential scan-

ning calorimetry (DSC) experiments were performed using a

CDR-4P thermal analyzer of Shanghai Balance Instrument fac-

tory under a flow of air atmosphere from 20 to 1000 °C. Lumi-

nescence spectra were measured at room temperature with an

Edinburgh FL-FS90 TCSPC system (UK).

2.2 Syntheses

Scheme 1 Constitutional formula and coordination

modes of H2BIC ligand

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DUAN Lin-Qiang et al.: Structures, Thermodecomposition Kinetics and Luminescence PropertiesNo.12

2.2.1 Synthesis of compound [Sm(HBIC)3]n (1)

A mixture containing SmCl3·6H2O (0.0365 g, 0.1 mmol),

H2BIC (0.0162 g, 0.1 mmol), NaOH (0.0040 g, 0.1 mmol), and

H2O (6 g, 333.6 mmol) was kept heating in a 10 mL stainless

steel reactor with a Teflon liner at 110 °C for 72 h. The reac-

tion system was then slowly cooled to room temperature at a

rate of 5 °C·h-1, and the colorless platy crystals were obtained,

washed with water, and dried in air. Yield: 42% based on

Sm(III). Anal. calcd. for C24H15N6SmO6 (Mr=633.77): C

45.48%, H 2.39%, N 13.26%; Found: C 45.43%, H 2.45%, N

13.35%. IR (KBr) ν/cm-1: 3122 (m), 3009 (m), 2919 (w), 2637

(w), 1642 (s), 1614 (vs), 1522 (s), 1460 (s), 1396 (vs), 1332

(s), 748 (s), 642 (m).

2.2.2 Synthesis of compound [Ho(HBIC)3]n (2)

Being followed the same procedure as for the preparation of

1 except that SmCl3·6H2O was replaced with HoCl3·6H2O

(0.0379 g, 0.1 mmol). The colorless platy crystals were ob-

tained, washed with water and dried in air. Yield: 40% based

on Ho(III). Anal. calcd. for C24H15N6HoO6 (Mr=648.35): C

44.46%, H 2.33%, N 12.96%; Found: C 45.37%, H 2.41%, N

12.92%. IR (KBr) ν/cm-1: 3119 (m), 3003 (m), 2922 (w), 2640

(w), 1647 (s), 1611 (vs), 1519 (s), 1456 (s), 1399 (vs), 1329

(s), 744 (s), 647 (m).

2.2.3 Synthesis of compound [Yb(HBIC)3]n (3)

Following the same procedure as for the preparation of com-

pound 1 but YbCl3·6H2O (0.0384 g, 0.1 mmol) was used in-

stead of SmCl3·6H2O. The white powders were obtained.

Yield: 35% based on Yb(III). Anal. calcd. for C24H15N6YbO6

(Mr=656.46): C 43.91% , H 2.30% , N 14.62% ; Found: C

43.80%, H 2.42%, N 14.55%. IR (KBr) ν/cm-1: 3115 (m), 3012

(m), 2925 (w), 2645 (w), 1644 (s), 1616 (vs), 1515 (s), 1465

(s), 1401 (vs), 1335 (s), 781 (s), 650 (m).

2.3 X-ray crystallography

Diffraction data for compounds 1 and 2 were collected on a

Bruker Smart Apex II CCD diffractometer (Germany)

equipped with graphite monochromated Mo Kα radiation (λ =

0.071073 nm) using ω and φ scan mode at 296(2) K. Absorp-

tion correction were applied using the SADABS program.

Their structures were solved by direct methods and refined

with full-matrix least-squares refinements based on F2 using

SHELXS-97 and SHELXL-97.23,24 All non-hydrogen atoms

were refined with anisotropic displacement parameters. Hydro-

gen atoms were placed in geometrically calculated positions.

Crystal data and structure refinement details for compounds 1

and 2 are summarized in Table 1, selected bond lengths and an-

gles are shown in Table S1 (see Supporting Information), and

hydrogen-bonding interactions are listed in Table S2 (see Sup-

porting Information).

3 Results and discussion3.1 Structure description

Powder X-ray diffraction indicates that compound 3 is iso-

morphous to compound 2 in Fig.S1 (see Supporting Informa-

tion). The structures of compounds 1 and 2 determined using

single-crystal X-ray diffraction, are isostructural, crystallizing

in monoclinic space group P21/n. Here, we take compound 1

for representative example to describe the structure of the coor-

dination compounds in detail. As shown in Fig.1, each Sm(III)

Table 1 Crystal data and structure refinement summary for compounds 1 and 2

Parameter

compound

empirical formula

formula weight

crystal system

space group

a/nm

b/nm

c/nm

α/(º)

β/(º)

γ/(º)

V/nm3

crystal size/mm3

Z

calculated density/(g·cm-3)

F(000)

μ/mm-1

Rint

data/restraints/parameters

goodness-of-fit on F2

final R indices [I＞2σ(I)]

R indices (all data)

Value

1

C24H15N6SmO6

633.77

monoclinic

P21/n

0.97729(10)

0.90060(9)

2.6032(3)

90

91.175(2)

90

2.2907(4)

0.28×0.26×0.04

4

1.838

1244

2.619

0.0612

4080/0/334

1.021

R1=0.0425, wR2=0.0820

R1=0.0619, wR2=0.0886

2

C24H15N6HoO6

648.35

monoclinic

P21/n

0.96853(8)

0.88829(8)

2.5899(2)

90

91.1070(10)

90

2.2277(3)

0.31×0.27×0.04

4

1.993

1264

3.609

0.0382

3980/0/334

1.074

R1=0.0322, wR2=0.0702

R1=0.0381, wR2=0.0729

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Acta Phys. ⁃Chim. Sin. 2012 Vol.28

ion center is eight-coordinated by three nitrogen atoms and

five carboxyl oxygen atoms from five HBIC- ligands, resulting

in a slightly distorted two-capped triangle prism geometry. The

Sm―O bond distances are in the range of 0.2351(4)-0.2497(4)

nm, and Sm―N bond lengths vary from 0.2535(5) to 0.2577

(5) nm, which are slightly longer than the lengths of Ho―O

[0.2302(3)-0.2461(3) nm] and Ho―N [0.2461(4)-0.2526(4)

nm] in compound 2. However, the bond angles of O―Sm―O

change from 70.79(14)° to 156.96(15)°, and the bond angles of

N― Sm―N range from 70.44(17)° to 151.91(17)° , slightly

smaller than those of O―Ho―O [70.26(11)°-157.13(12)° ]

and N―Ho―N [71.16(13)°-152.70(13)°] in compound 2 (Ta-

ble S1). The tiny differences may be ascribed to the effect of

lanthanide contraction and soft and hard acid-alkali.

Further analysis reveals that the partly deprotonated HBIC-

exhibits two coordination modes, as shown in Scheme 1. Mode

I adopts a simple N,O-bidentate-chelating fashion, and Mode

II features a µ2-bridge fashion connecting two Sm(III) ions, in

which one Sm(III) ion is coordinated one imidazole N atom

and one carboxyl O atom in N,O-bidentate motif, and the other

Sm(III) ion is monodentatly bonded by the other carboxyl O at-

om. As shown in Fig.2(a), the adjacent Sm(III) centers are

bridged by HBIC- ligands with Mode II to generate a 2D struc-

ture, where some HBIC- ligands with Mode I just chelate the

Sm(III) ions to stable the configuration of the metal centers

and the whole network. The topological analysis method was

used to describe intuitively and understand the structural char-

acteristics of compound 1, as illustrated in Fig.2(b), the 2D

framework can be simplified to be a (4,4) net through defining

the Sm(III) centers as knots and HBIC- ligands as spacers. In

the net, the size of each grid is 0.67171(6) nm×0.69699(7) nm,

which is larger than that in compound 2 [0.66425(5) nm ×

0.68974(5) nm].

Notably, another obvious structural feature of compound 1 is

the existence of the strong hydrogen bonds between the carbox-

ylate groups and imidazole rings [N(6) ― H(6N)···O(6)#1,

0.2818(7) nm, N(3) ― H(3)···O(5)#2, 0.2788(7) nm, and

N(2)―H(2)···O(1)#3, 0.2723(6) nm (#1: -x+1, -y+1, -z; #2: -x+

1/2, y+1/2, -z+1/2; #3: -x+3/2, y+1/2, -z+1/2)] (Table S2),

which are crucial for stabilizing the whole structure of com-

pound 1. These abundant hydrogen bonds eventually link the

2D layers into a 3D supramolecular framework (Fig.3).

3.2 IR spectrum

In the IR spectra of compounds 1-3, the powerful peaks at

approximately 1640, 1610, 1520, 1460, and 750 cm-1 can be as-

cribed to the asymmetric and symmetric stretching vibrations

of carboxyl and phenyl groups from the H2BIC ligands. The re-

spective values of the vas(COO-) (182 cm-1) and vs(COO-) (198

Fig.1 Coordination environment and coordination polyhedron geometry of Sm(III) in compound 1

Fig.2 (a) 2D network of compound 1 and (b) simplified 2D structure with (4,4) topologyAll H atoms and partial ligands in (a) are omitted for clarity.

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DUAN Lin-Qiang et al.: Structures, Thermodecomposition Kinetics and Luminescence PropertiesNo.12

cm-1) clearly indicate that the carboxylate groups are coordinat-

ed with the metal ions in both monodentate and bidentate-che-

lating coordination modes.25 In addition, the characteristic ab-

sorption bands at approximately 3120 and 1610 cm-1 represent

the N ― H and C＝N stretching vibrations from imidazole

rings, respectively.

3.3 Thermogravimetric analysis

In order to evaluate the stability of the coordination com-

pounds, the thermalgravimetric (TG) analyses were carried out

between 20 and 1000 °C at a heating rate of 10 °C·min-1 under

air atmosphere. TG data of compounds 1-3 plotted in Fig.4

possess similar thermal decomposition process, which further

demonstrates that the frameworks 1-3 are isostructural. Com-

pound 1 is taken for a representative example to study the ther-

mostability of the coordination compounds. TG curve of com-

pound 1 indicates that compound 1 could be stable up to 360 °C,

showing high thermal stability. Then one continuous mass loss

of 74.25% occurred in the range 360-700 ° C is attributed to

the decomposition of the framework. The observed residual is

25.75%, which is nearly in agreement with the calculated value

of 27.50%. The final solid powder is identified as Sm2O3.

3.4 Non-isothermal thermoanalysis kinetics

As observed from TG curve, compound 1 is transformed in-

to Sm2O3 in one process. From equations (1) and (2), thermode-

composition kinetics parameters of the apparent activation en-

ergy (E) and the pre-exponential factor (A) of the process were

determined by two most common Kissinger and Ozawa-Doyle

methods.26,27

The Kissinger and Ozawa-Doyle equations are as follows,

respectively:Eβ

RT 2p

= A exp(- ERTp

) (1)

lg β + 0.4567ERTp

= C (2)

where, Tp is the peak temperature, R is the gas constant, β is the

linear heating rate, and C is constant.

Herein, the non-isothermal kinetics analysis of compound 1

is discussed based on DSC curves at different heating rates. In

viewed of the exothermic peak temperatures measured at four

different heating rates of 5, 10, 15, and 20 ° C·min-1 (Fig.5),

Kissinger and Ozawa-Doyle methods are applied to explore

the kinetics parameters of the compound [Sm(HBIC)3]n. The

relevant parameter values are calculated and listed in Table 2,

it is obvious to notice that EK and EO are 199.3 and 205.2 kJ·mol-1, respectively, which is of seemly significance to evaluate

the process by thermoanalysis kinetics method when com-

pound 1 could be employed as precursor for preparation of

Sm2O3 with different morphologies and sizes.

3.5 Photoluminescent property

The luminescent properties of compounds 1 and 3 were in-

vestigated in the solid state at room temperature. As shown in

Fig.6(b), the emission spectrum of compound 1 exhibits a se-

ries of sharp lines characteristic of the Sm(III) energy-level

structure upon excitation at 348 nm (Fig.6(a)). The characteris-

tic emission bands of Sm(III) ion centered at 565, 595, 643,

702 nm are attributed to the transitions of 4G5/2→6HJ/2 (J=5, 7, 9,

Fig.3 3D network in compound 1 constructed by N―H···O

hydrogen-bonding interactions

Fig.4 TG curves of compounds 1-3

Fig.5 DSC curves of [Sm(HBIC)3]n at different heating rates

Table 2 Peak temperatures of the exothermic stage at different

heating rates and the thermoanalysis kinetic parameters

RK and EK are the linear correlation coefficient and apparent activation energy

calculated by Kissinger method, respectively. RO and EO are the linear correlation

coefficient and apparent activation energy calculated by Ozawa-Doyle

method, respectively.

β/(°C·min-1)

5

10

15

20

Tp/°C

422

444

456

476

lg(AK/s-1)28

8.1091

RK

0.9862

RO

0.9838

EK/(kJ·mol-1)

199.3

EO/(kJ·mol-1)

205.2

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Acta Phys. ⁃Chim. Sin. 2012 Vol.28

11, respectively).29,30 The 4G5/2→6H5/2 (565 nm) transition con-

sists of the relatively weak band observed in the spectrum,4G5/2→6H7/2 (595 nm) starts as a shoulder then splits into two

poor-defined peaks but is the most intense observed in the spec-

trum, and the 4G5/2→6H9/2 transition is also a poorly resolved

peak at 643 nm.31 Yb(III) is a special example among the

near-infrared-emitting lanthanide ions, because Yb(III) ion has

only one excited 4f level, namely, the 2F5/2 level. Hence, under

excitation of 752 nm (Fig.6(c)), the broad emission spectrum

of compound 3 (Fig.6(d)) is observed in the range 900-1050

nm at λmax=972 nm, which is assigned to the characteristic tran-

sition of 2F5/2→2F7/2.32 Both the characteristic lanthanide emis-

sion bands observed in compounds 1 and 3 reveal that the

HBIC- ligand shows good sensitization for lanthanide lumines-

cence, suggesting compounds 1 and 3 could be anticipated as

optical materials.

4 ConclusionsIn summary, three new compounds [Ln(HBIC)3]n [Ln=Sm

(1), Ho (2), Yb (3)] were hydrothermally synthesized and char-

acterized. In their isomorphous structures, the HBIC- ligands

connect lanthanide ions with two new coordination modes to

form 2D planes, which are further assembled into 3D supramo-

lecular frameworks through strong hydrogen-bonding interac-

tions. TG analyses indicate that compounds 1-3 exhibit good

thermostability. The apparent activation energy of thermode-

composition of the compound 1, EK and EO were respectively

determined to be 199.3 and 205.2 kJ·mol-1 by the Kissinger

and Ozawa-Doyle methods. Luminescent property investiga-

tions indicate that compounds 1 and 3 exhibit characteristic

transitions in visible and near-infrared regions, respectively,

suggesting that the HBIC- ligand is a good sensitizer for lantha-

nide ions luminescence.

Supporting Information: available free of charge via the in-

ternet at http://www.whxb.pku.edu.cn.

References(1) Lv, Y. K.; Zhan, C. H.; Feng, Y. L. CrystEngComm 2010, 12,

3052. doi: 10.1039/b925546j

(2) Lv, Y. K.; Zhan, C. H.; Jiang, Z. G.; Feng, Y. L. Inorg. Chem.

Commun. 2010, 13, 440. doi: 10.1016/j.inoche.2010.01.007

(3) Halder, G. J.; Kepert, C. J.; Moubaraki, B.; Murray, K. S.;

Cashion, J. D. Science 2002, 298, 1762. doi: 10.1126/

science.1075948

(4) Min, K. S.; Suh, M. P. J. Am. Chem. Soc. 2000, 122, 6834. doi:

10.1021/ja000642m

(5) Dong, Y. B.; Jiang, Y. Y.; Li, J.; Ma, J. P.; Liu, F. L.; Tang, B.;

Huang, R. Q.; Batten, S. R. J. Am. Chem. Soc. 2007, 129, 4520.

doi: 10.1021/ja0701917

(6) Sudik, A. C.; Millward, A. R.; Ockwig, N. W.; Côté, A. P.; Kim,

J.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 7110. doi:

10.1021/ja042802q

(7) Bünzli, J. C. G.; Piguet, C. Chem. Rev. 2002, 102, 1897. doi:

10.1021/cr010299j

Fig.6 Luminescence excitation and emission spectra of compounds 1 and 3 in the solid state at room temperature

2788

DUAN Lin-Qiang et al.: Structures, Thermodecomposition Kinetics and Luminescence PropertiesNo.12

(8) Dias, A. D. B.; Viswanathan, S. Chem. Commun. 2004, 1024.

(9) Ronson, T. K.; Lazarides, T.; Adams, H. Chem. Eur. J. 2006, 12,

9299. doi: 10.1002/chem.200600698

(10) Yu, Y. Y.; Liu, J. F.; Li, H. Q.; Zhao, G. L. Acta Phys. -Chim.

Sin. 2010, 26, 1535. [余玉叶, 刘建风, 李花琼, 赵国良. 物理

化学学报, 2010, 26, 1535.] doi: 10.3866/PKU.WHXB20100622

(11) Zhu, W. H.; Wang, Z. M.; Gao, S. Inorg. Chem. 2007, 46, 1337.

doi: 10.1021/ic061833e

(12) Ying, S. M.; Mao, J. G. Cryst. Growth Des. 2006, 6, 964. doi:

10.1021/cg050554j

(13) Do, K.; Muller, F. C.; Muller, G. J. Phys. Chem. A 2008, 112,

6789. doi: 10.1021/jp804463e

(14) Long, D. L.; Blake, A. J.; Champness, N. R.; Wilson, C.;

Schröder, M. Angew. Chem. Int. Edit. 2001, 40, 2443.

(15) Long, D. L.; Hill, R. J.; Blake, A. J.; Champness, N. R.;

Hubberstey, P.; Proserpio, D. M.; Wilson, C.; Schröder, M.

Angew. Chem. Int. Edit. 2004, 43, 1851. doi: 10.1002/anie.

200352625

(16) Cui, Y.; Ngo, H. L.; White, P. S.; Lin, W. Chem. Commun. 2002,

1666.

(17) Qin, C.; Wang, X. L.; Wang, E. B.; Su, Z. M. Inorg. Chem.

2005, 44, 7122. doi: 10.1021/ic050906b

(18) Zhang, M. B.; Zhang, J.; Zheng, S. T.; Yang, G. Y. Angew.

Chem. Int. Edit. 2005, 44, 1385. doi: 10.1002/anie.200461424

(19) Wagner, E.; Wittmann, H. J.; Elz, S.; Strasser, A. Bioorg. Med.

Chem. Lett. 2011, 21, 6274. doi: 10.1016/j.bmcl.2011.09.001

(20) Nandhakumar, R.; Soo, A. Y.; Hong, J.; Ham, S.; Kim, K. M.

Tetrahedron 2009, 65, 666. doi: 10.1016/j.tet.2008.11.022

(21) Zheng, S. R.; Cai, S. L.; Fan, J.; Xiao, T. T.; Zhang, W. G. Inorg.

Chem. Commun. 2011, 14, 818. doi: 10.1016/j.inoche.

2011.02.017

(22) Fan, J.; Cai, S. L.; Zheng, S. R.; Zhang, W. G. Acta Crystallogr.

Sect. C: Cryst. Struct. Commun. 2011, 67, m346.

(23) Sheldrick, G. M. SHELXS-97, Program for Solution of Crystal

Structures; University of Gottingen: Germany, 1997.

(24) Sheldrick, G. M. SHELXL-97, Program for Refinement of

Crystal Structures; University of Gottingen, Germany, 1997.

(25) Nakamoto, K. Infrared Spectra and Raman Spectra of Inorganic

and Coordination Compounds; Wiley VCH: New York, 1986.

(26) Kissinger, H. E. Anal. Chem. 1957, 29, 1702. doi: 10.1021/

ac60131a045

(27) Ozawa, T. Bull. Chem. Soc. Jpn. 1965, 38, 1881. doi: 10.1246/

bcsj.38.1881

(28) Hu, R. Z.; Gao, S. L.; Zhao, F. Q.; Shi, Q. Z.; Zhang, T. L.;

Zhang, J. J. Thermal Analysis Kinetics; Science Press: Beijing,

2007. [胡荣祖, 高胜利, 赵风起, 史启祯, 张同来, 张建军. 热

分析动力学. 北京: 科学出版社, 2007.]

(29) Su, S. Q.; Chen, W.; Qin, C.; Song, S. Y.; Guo, Z. Y.; Li, G. H.;

Song, X. Z.; Zhu, M.; Wang, S.; Hao, Z. M.; Zhang, H. J. Cryst.

Growth Des. 2012, 12, 1808. doi: 10.1021/cg201283a

(30) Liu, M. S.; Yu, Q. Y.; Cai, Y. P.; Su, C. Y.; Lin, X. M.; Zhou, X.

X.; Cai, J. W. Cryst. Growth Des. 2008, 8, 4083. doi: 10.1021/

cg800526y

(31) Li, Z. F.; Yu, J. B.; Zhou, L.; Zhang, H. J.; Deng, R. P. Inorg.

Chem. Commun. 2008, 11, 1284. doi: 10.1016/j.inoche.

2008.08.008

(32) Huang, W.; Wu, D. Y.; Zhou, P.; Yan, W. B.; Guo, D.; Duan, C.

Y.; Meng, Q. J. Cryst. Growth Des. 2009, 9, 1361. doi: 10.1021/

cg800531y

2789