Hydrothermal synthesis, crystal structure and properties of Ag(I) …pfsmet/papers/A1_40_2010...

Hydrothermal synthesis, crystal structure and properties of Ag(I)-4f compounds based on 1H-benzimidazole - 5, 6 -

dicarboxylic acid

Journal: Dalton Transactions

Manuscript ID: DT-ART-05-2010-000579.R1

Article Type: Paper

Date Submitted by the Author:

22-Aug-2010

Complete List of Authors: Sun, Yaguang; Shenyang University of Chemical Technology,

Laboratory of Coordination Chemistry Wu, Yongli; Shenyang Institute of Chemical Technology, Laboratory of Coordination Chemistry Xiong, Gang; Shenyang Institute of Chemical Technology, Laboratory of Coordination Chemistry Smet, Philippe F; Ghent University, LumiLab, Department of Solid State Sciences Ding, Fu; Shenyang Institute of Chemical Technology, Laboratory of Coordination Chemistry Guo, Meiyan; Shenyang Institute of Chemical Technology, Laboratory of Coordination Chemistry

Zhu, Mingchang; Shenyang Institute of Chemical Technology, Laboratory of Coordination Chemistry gao, enjun; Shenyang Institute of Chemical Technology Dirk, Poelman; Ghent University, LumiLab, Department of Solid State Sciences Verpoort, Francis; Ghent University, Inorganic and Physical Chemistry

Dalton Transactions - For Review Only

1

Hydrothermal synthesis, crystal structure and properties of

Ag(I)-4f compounds based on 1H-benzimidazole - 5, 6 -

dicarboxylic acid

Ya-guang Suna*, Yong-li Wua, Gang Xionga, Philippe F. Smetb, Fu Dinga, Mei-yan Guoa,

Ming-chang Zhua, En-jun Gaoa, Dirk Poelmanb, Francis Verpoortc

aLaboratory of Coordination Chemistry, Shenyang Institute of Chemical Technology, Shenyang,

100142, China

b LumiLab, Department of Solid State Sciences, Ghent University, Ghent, 9000, Belgium

cOrganometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent

University, Ghent, 9000, Belgium

Abstract: Seven novel heterometallic coordination polymers [CeAg(Hbidc)2(H2O)2](1) and

[LnAg(Hbidc)2]·3(H2O)[Ln=Sm(2), Gd(3), Tb(4), Dy(5), Ho(6), Er(7), H3bidc =

1H-benzimidazole-5,6-dicarboxylic acid] have been synthesized under hydrothermal conditions

and characterized by elemental analysis, FT-IR, TG analysis, and single crystal X-ray diffraction.

X-ray analysis revealed that the seven complexes present two different types of three-dimensional

(3D) structures. Complex 1 crystallized in an orthorhombic manner having a Pna2(1) space group,

consisting of a 3D framework with a 1D heterometallic chain. Polymers 2-7 are isostructural and

crystallized in an orthorhombic fashion having a Pccn space group existing of a two-fold

interpenetrating 3D framework. The luminescence properties and the magnetic properties of all

polymers were investigated.

Introduction

The assembly of d-f heterometallic coordination polymers (HMCPs) through rational design is

of great interest to crystal engineering not only because of their fascinating structural topology, but

also for their potential applications as functional materials in luminescence, molecular adsorption,

bimetallic catalysis and magnetism. 1-2 Considerable progress has been made in designing and

Page 1 of 35 Dalton Transactions - For Review Only

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fabricating d-f HMCPs, from 1D chains, 2D lattices to 3D frameworks. 3-5 The synthesis of d-f

HMCPs is still a challenging task since lanthanide ions have different coordination characteristics

compared to transition metals ions. Lanthanide ions behave as hard acids, having a preference for

oxygen to nitrogen donors. In contrast, d-block metal ions are borderline acids, having a strong

tendency to coordinate to N-donors, often resulting in homometallic coordination polymers rather

than d-f heterometallic coordination polymers.6 Hence, selection or design of a suitable ligand

containing an active coordination ability to both lanthanide ions and transition metal ions is crucial

for the construction of d–f heterometallic frameworks.7 In addition other parameters influencing

the synthesis of HCMPs, e.g. temperature, solvent, template and the pH have to be taken into

account.6c-8 In literature most of the investigations dealing with 3d–4f HCMPs, reporting on

systems such as Ln-Mn, Ln-Fe, Ln-Pt, Ln-Co and Ln-Cu systems bridged by the N-heterocyclic

carboxylate ligands.7a,9-12 With respect to 4d-4f HMCPs, it is worth to notice that previous studies

revealed the following features: (i) The reported 4d-4f HMCPs have 1D chains, 2D lattices or 3D

frameworks, but only as interpenetrating structures. (ii) These studies almost exclusively applied

isonicotinic ligands, and almost totally ignore the use of other carboxylate ligands.2a,2b,4a,13

On the other hand, an important property of coordination polymer frameworks is their

tendency to form entangled structures in which two or more independent infinite networks

interpenetrate each other14. Interpenetration can be utilized to strengthen the interaction between

the gaseous molecule and the framework by an entrapment mechanism in which a hydrogen

molecule is in close proximity with several aromatic rings to from interpenetrating networks15-16.

Although many intriguing structures containing interpenetration have been constructed and

discussed17, most of them are monometallic coordination polymers. Consequently, controll of the

architecture of interpenetrating HCMPs is an interesting research branch of crystal engineering.

Recently, our group focused on the application of imidazole carboxylic acid ligands as

multidentate ligands. We have reported on Sm-Mn and Eu-Ag HMCPs18 implementing

1H-imidazole-4,5-dicarboxylate. In the present work, 1H-benzimidazole-5,6-dicarboxylic acid

(H3bidc) was the multidentate ligand of choise for the following reasons: (i) It was observed that

the bridging angle M-Im-M (where M = metal ions and Im = imidazolate) coincides with that of

the Si-O-Si angle in zeolites (145°), giving rise to many new zeolitic imidazolate frameworks

(ZIFs).19 The latter can be applied in CO2 captation and selective separation of industrially

Page 2 of 35Dalton Transactions - For Review Only

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relevant gas mixtures.20 (ii) H3bidc is a multidentate and rigid ligand with multiproton

donor-acceptor sites, the bidc3- anion possesses two nitrogen atoms and four oxygen atoms giving

rise to a variety of coordinations, such as monodentate, chelating, bidentate bridging, monodentate

bridging and chelate bridging. Moreover, the collaboration of the two carboxylate groups of the

bidc3- anion might connect metal magnetic centers serving as mediators of magnetic exchange;21

(iii) Compared with the ligand 1H-imidazole-4,5-dicarboxylate, an extended π-conjugated system

is introduced by applying H3bidc, resulting in possible novel structures and properties.

Furthermore, the soft silver (I) ion easily coordinate with the N-donor atoms with linear, trigonal

and tetrahedral coordination environments. These are favorable building blocks for the

construction of coordination polymer frameworks22. Based on the aforementioned points, our aim

is to synthesize novel Ln-Ag HMCPs with noteworthy properties by using Ln(NO3)3·6H2O,

AgNO3 and H3bidc ligands. In this paper, a systematic investigation of seven Ln-Ag HMCPs

under hydrothermal reaction was performed: [CeAg(Hbidc)2(H2O)2] (1) and

[LnAg(Hbidc)2]·3(H2O) [Ln = Sm(2), Gd(3), Tb(4), Dy(5), Ho(6), Er(7)]. To the best of our

knowledge, complexes 2-7 are rare examples of two-fold interpenetrating 4d-4f HMCPs. The

successful preparation of the seven coordination polymers provides valuable information for

further construction of interpenetrating 4d-4f 3D HMCPs. The complexes were fully characterized

and the luminescence properties of complexes 1 - 7 were analyzed, they exhibit the characteristic

transitions of the corresponding lanthanide ions. Magnetic tests of complexes 1-7 were carried out

and the result reveals an antiferromagnetic coupling in complex 3.

Experimental Section

Materials. All chemicals purchased were of reagent grade and used without further

purification. All syntheses were carried out in 23 mL Teflon-lined autoclaves under autogenous

pressure. The reaction vessels were filled to approximately 50% volume capacity. Water used in

the synthesis was distilled before use.

Physical Measurements. The elemental analyses (C, H, and N) were carried out applying a

Perkin-Elmer 240C elemental analyzer; FT-IR spectra were recorded on a Nicolet IR-470

spectrometer using KBr pellets. Powder X-ray diffraction (PXRD) patterns of the samples were

recorded using an X-ray diffractometer (BRUKER D8 ADVANCE) with Cu Kα radiation.

Thermogravimetric analyses (TGA) experiments were performed on a NETZSCH TG 209

instrument with a heating rate of 5 °C min-1. Luminescence spectra were recorded on a FS920

steady state fluorescence spectrometer (Edinburgh Instruments) equipped with a Hamamatsu


4

R928P red-sensitive photomultiplier (wavelength range from 200 to 850 nm) and a Ge infrared

detector (700–1600 nm). Luminescence decay measurements were obtained with a pulsed nitrogen

laser (excitation wavelength of 337nm, pulse length of 800ps, repetition rate of 1Hz) and a

1024-channel Intensified CCD (Andor Technology) attached to a 0.5 m Ebert monochromator.

Variable-temperature magnetic susceptibilities were measured on a Quantum Design MPMS-7

SQUID magnetometer. Diamagnetic corrections were made with Pascal’s constants for all

constituent atoms.

X-ray Crystallographic Study. The collection of single crystal crystallographic data was carried

out on a Bruker SMART Apex CCD diffractometer using graphite-monochromated Mo Kα

radiation (0.71073 Å) at 293 K in the ω-2θ scan mode. An empirical absorption correction was

applied to the data using the SADABS program. The structures were solved by direct methods and

refined by full-matrix least-squares methods on F2 using the SHELXTL crystallographic software

package23. All non-H atoms were refined anisotropically. The H atoms were placed in calculated

positions and refined by using a riding mode. For 1, refinement in as an orthorhombic space group

Pna2(1) using a racemic twin model and employing the TWIN and BASF instructions resulted in

a in a BASF (relative batch scale factor) of 0.5. The crystallographic data, selected bond lengths

and angles for 1-7 are listed in Tables 1 and 2.

Synthesis of [CeAg (Hbidc)2(H2O)2] (1). A mixture of Ce(NO3)3·6H2O (0.2 mmol), AgNO3

(0.2 mmol), H3bidc (0.2mmol), and water (10 mL) was sealed in a 23 mL Teflon reactor and was

kept under autogenous pressure at 170 °C for 5 days, then cooled to room temperature during 3

days. Light-yellow square-shaped crystals were filtered off, washed with distilled water and dried

in air. Finally, 0.1052 g (76% yield based on Ce(NO3)3) crystals were obtained. The

as-synthesized material is insoluble in water and common organic solvents. Elem. anal. Calcd. for

C18 H12 AgCeN4 O10 (%): C, 31.22; H, 1.74; N, 8.09. Found: C, 30.13; H, 1.68; N, 8.02. IR

spectrum (KBr, cm-1): 3396m, 3157m, 1748w, 1631w, 1538s, 1476m, 1419s, 1373s, 1278m,

1144m, 962w, 893w,875m, 822m, 792m, 760w, 725w, 705w, 613m, 521w, 468w.

Synthesis of [SmAg(Hbidc)2]·3(H2O) (2). A procedure identical with 1 was followed to

prepare 2 except Ce(NO3)3·6H2O was replaced by Sm(NO3)3·6H2O (0.2 mmol). Light yellow

square-shaped crystals were obtained with a yield of 0.1038g (72% yield based on Sm(NO3)3).

Elem. anal. Calcd. for C18 H14 Ag Sm N4 O11(%): C, 30.00; H, 1.95; N, 7.77. Found: C, 30.05;


5

H, 1.94; N, 7.75. IR spectrum (KBr, cm-1): 3384m, 3122m, 1559s, 1489s, 1429s, 1277w, 1125w,

882w, 819w, 793m,759w.

Synthesis of [GdAg(Hbidc)2]·3(H2O) (3). A procedure identical with 1 was followed to

prepare 3 except that Ce(NO3)3·6H2O was replaced by Gd(NO3)3·6H2O (0.2 mmol). Colorless

square-shaped crystals were obtained with a yield of 0.1222g (84% yield based on Gd(NO3)3).

Elem. Anal. Calcd. for C18 H14Ag Gd N4 O11 (%): C, 29.72; H, 1.94; N, 7.70. Found: C, 29.75;

H, 1.87; N, 7.67. IR spectrum (KBr, cm-1): 3384m,3127m, 1542s, 1476s, 1423s, 1277w, 1130w,

881w, 819w, 796m, 762w.

Synthesis of [TbAg(Hbidc)2]·3(H2O) (4). A procedure identical with 1 was followed to

prepare 4 except thet Ce(NO3)3·6H2O was replaced by Tb(NO3)3·6H2O (0.2 mmol). Colorless

square-shaped crystals were obtained with a yield of 0.1052g(79% yield based on Tb(NO3)3).

Elem. anal. Calcd. for C18 H14 AgTb N4 O11 (%): C, 29.65; H, 1.94; N, 7.68. Found: C, 29.60;

H, 1.88; N, 7.63. IR spectrum (KBr, cm-1): 3388m, 3132m, 1542s, 1489m, 1424s, 1280w,

1122w,885w, 815w, 791s, 753w.

Synthesis of [DyAg(Hbidc)2]·3(H2O) (5). A procedure identical with 1 was followed to

prepare 5 except that Ce(NO3)3·6H2O was replaced by Dy(NO3)3·6H2O (0.2 mmol). Colorless

square-shaped crystals were obtained with a yield of 0.0952g (65% yield based on Dy(NO3)3).

Elem. anal. Calcd. for C18 H14 Ag Dy N4 O11(%): C, 29.51; H, 1.93; N, 7.65. Found: C, 29.55;

H, 1.84; N, 7.64. IR spectrum (KBr, cm-1): 3386m, 3125m, 1560s, 1474s, 1426s, 1279w, 1127w,

881w, 815w 799m, 760w.

Synthesis of [HoAg(Hbidc)2]·3(H2O) (6). A procedure identical with 1 was followed to

prepare 6 except that Ce(NO3)3·6H2O was replaced by Ho(NO3)3·6H2O(0.2 mmol). Colorless

square-shaped crystals were obtained with a yield of 0.1323g (90% yield based on Ho(NO3)3).

Elem. anal. Calcd. for C18 H14Ag Ho N4 O11(%): C, 29.40; H, 1.92; N, 7.63. Found: C, 29.38; H,

1.84; N, 7.65. IR spectrum (KBr, cm-1): 3376m, 3129m, 1559s, 1476s, 1428s, 1280m, 1126m,

880w, 805m, 785m, 754w.

Synthesis of [ErAg(Hbidc)2]·3(H2O) (7). A procedure identical with 1 was followed to

prepare 7 except that Ce(NO3)3·6H2O was replaced by Er(NO3)3·6H2O (0.2 mmol). Pink

square-shaped crystals were obtained with a yield of 0.1180g (80% yield based on Er(NO3)3).

Elem anal. Calcd for C18 H14 Ag Er N4 O11(%): C, 29.32; H, 1.91; N, 7.60. Found: C, 29.2; H,


6

1.94; N, 7.70. IR spectrum (KBr, cm-1): 3379m, 3130m, 1539s, 1472s, 1423s, 1290m, 1222w,

882w,815w 790w, 753w.

Results and Discussion

[CeAg(Hbidc)2(H2O)2] (1) An ORTEP view of 1 (Figure 1) shows that the Ce(III) center is

coordinated with ten oxygen atoms, eight oxygen atoms derived from four carboxylate groups

with chelating modes and two oxygen atoms derived from water molecules (Figure 1). The

Ce(III)-O distances range from 2.522(3) to 2.773Å, the average bond length of Ce(III)–O is

2.605(4)Å, similar to the reported Ce(III)-O distance 2.588Å,24 the O-Ce(III)–O bond angles vary

from 48.68(11) to 175.78(11)°. Concerning the Ag(I) ion, it exhibits a trigonal geometry, being

coordinated by two nitrogen atoms from two different Hbidc2- ligands (Ag(I)–N(2)#3, 2.171(4) Å ;

Ag(I)-N(3)#4, 2.173(4)Å) and an oxygen atom from one carboxylate group (Ag(I)–O6,

2.545(3)Å). Since the H3bidc ligands posses a wide variety of coordination motifs, a schematic

representation of the different coordination modes is depicted in scheme 1. In complex 1, the

H3bidc ligands exhibit two new bridging modes which have not been reported previously (scheme

1, k and l): One acts as µ3 bridge between two Ce(III) ions and one Ag(I) ion; the other one acts as

µ4 link between two Ce(III) ions and two Ag(I) ions. Based on these coordination modes of the

H3bidc ligands, a one-dimensional heterometallic chain with Ce(III)-Ag(I) connections is formed

(Figure 2). All the Ce(III) centers are linked by double carboxylate bridges and Ag(I) centers are

anchored to the Ce(III)-carboxylate chain through Ag-N bonds of the benzimidazole ring. This

type of construction is unusual in the field of heterometallic coordination polymers.

The one-dimensional heterometallic chains are joined together by carboxylate groups of the

Hbidc2- ligand to form two-dimensional nets that is further connected by Ag(I)-O bonds,

resulting in the overall 3D framework. The topological approach is a good way to understand the

nature of the involutes framework as it could lead to reduced multidimensional structures. Based

on the topological approach of the simplification principle, the Ag(I) ion can be defined as

3-connected nodes and the Ce(III) ion can be defined as 4-connected nodes, the Hbidc2- ligand can

be defined as 3-connected and 4-connected nodes. Consequently, the topological mode of 1 can be

described as a 3,3,4,4-connected{4.82}{4.84.10} topological framework, as depicted in Figure 4.

Furthermore, π-π interaction occurs between benzimidazole rings of Hbidc2- in the frameworks

giving extra stability to the 3D heterometallic framework, the centroid distances are 3.520 and


7

3.520 Å, respectively.

[LnAg (Hbidc)2]·3(H2O) [Ln = Sm(2), Gd(3), Tb(4), Dy(5), Ho(6), Er(7)] Since 2-7 are

isostructural and crystallize in an orthorhombic manner with space group Pccn, only structure 5 is

described in detail as a typical example. An ORTEP view of polymer 5 is shown in Figure 5, there

are one Dy(III) ion, one Ag(I) ion and two crystallographically unique Hbidc2- ligands in one

asymmetric unit of 5. The center Dy(III) ion is eight coordinated by one chelating bidentate

carboxylate group (O5 and O6), five di-monodentate carboxylate groups (O3, O1, O5A, O2A and

O4A), and a monodentate carboxylate group (O8A), which provide a distorted

square-antiprismatic coordination geometry. The bond length of Dy(III)–O ranges from 2.290(3)

to 2.543(3)Å, the average bond length of Dy(III)–O is 2.358(3)Å, the O–Dy(III)–O bond angle

ranges between 68.73(11)° and 152.17(11)°. The Ag(I) center is coordinated by two nitrogen

atoms from two Hbidc2- ligands (Ag(I)–N1, 2.129(4)Å and Ag(I)–N4A, 2.124(4)Å), the

coordination geometry of the Ag(I) ion can be described as a distorted linear geometry

( N1–Ag(I)–N4A is 168.49(15)°). It is appealing that there are two types of Hbidc2- ligands with

different conformation and binding modes, (scheme 1, m and n): one behaves as µ4-Hbidc2- mode

linking three Dy(III) ions and one Ag(I) ion (Scheme l, m); the other acts as µ3-Hbidc2- mode

connecting two Dy(III) ions and one Ag(I) ion with two bidentate and one monodentate mode

(Scheme 1, n). Accordingly, the Dy(III) ions are associated together through µ2-O7 and two

carboxylate groups to give rise to the Dy(COO)4- rod substructure along the y-direction (Figure 6),

in which the distance of adjacent Dy(III) is 4.452Å. Further, the rod substructures were linked by

the fragments of Hbidc2- ligands and Ag(I) to create the four-connecting rod 3D packing

architecture, as depicted in Figure 7a.

It is interesting that the overall framework contains two sets of frameworks. Each set exists of a

one-dimensional rectangular channel along the y-direction and a considerable void space remains

(ca. 411.4Å3, equal to 10.8% of the cell volume)25 (Figure 7b). Uncoordinated water molecules act

as guest molecules and further fill in its residual void. According to the simplification principle of

the topological analysis, Dy(III) ions can be defined as 5-connected nodes and the Ag(I) can be

defined as a line, Hbidc2- ligands can be defined as 3-connected and 4-connected nodes. As a

result, compound 5 reveals a 3, 4, 5-connection with {4.82}{42.6.82.10}{46.64} topological 3D

framework, the topological mode is shown in Figure 8. To our knowledge, this is a rare example


8

of 4d-4f heterometallic coordination polymers with a 3, 4, 5-connected two-fold interpenetrating

3D framework .

The Ln-O bond length of these seven compounds declines with decreasing radii of the Ln ion

and vary from 2.6054(1) to 2.3556(6)Å. This phenomenon can be attributed to the lanthanide

contraction effect.

TGA and PXRD

TGA was carried out using polycrystalline samples of 1-7 in a temperature range of 20-550°C

(Figure 9). The first weight loss of polymer 1 from 80 to 170°C amounts to 5.50%, corresponding

to the loss of the two coordinating water molecules (calcd. 5.20%). From 170 to 420°C, the weight

loss 54.30% (calcd 54.36%) is attributed to the removal of organic moieties. Above 420°C, there

is almost no mass modification, Ce2O3 and Ag2O were obtained representing the remaining mass,

40.51% (calcd 40.44%). For 2, the first weight loss takes place between 95 and 210°C, the total

weight lost in this temperature range is 7.55% corresponding to the loss of three uncoordinated

water molecules (calcd. 7.49%). The subsequent weight loss, 51.74%, occurred from 270 to 458°C,

which was due to the loss of the Hbidc2- ligand (calcd. 51.69%), and finally Sm2O3 and Ag2O

were obtained. TGA analyses for 3-7 are comparable with the analysis of 2.

Powder X-ray diffraction (PXRD) analysis of polymers 1-7 has been performed at room

temperature (See Support Information). The perceived patterns for 1-7 are in good agreement with

the calculated patterns obtained from the single-crystal structures. This confirms that the

single-crystal structure is really representative of the bulk for the corresponding samples.

Luminescent properties

Compounds 2, 4 and 5 show emission spectra typical for the 4f-4f transitions, as encountered in

most trivalent lanthanide ions, and their photoluminescence emission and excitation spectra are

depicted in Figure 10. The emission spectra are dominated by 4f-4f transitions from the rare earth

ions Sm3+, Tb3+ and Dy3+, respectively. For 2, the emission lines are situated in the red part of the

visible spectrum resulting from the transitions from the 4G5/2 excited state to the 6HJ levels, with J

= 5/2, 7/2, 9/2, 11/2 for the emission peaks at 561nm, 595nm, 642nm and 704nm respectively. For

4, the emission spectrum is dominated by the 545nm emission line, following the 5D4 to 7F5

transition. The other emission lines are originating from the same excited state and terminating at

the 7FJ manifold. For 5, three main emission peaks are found at 482nm, 575nm and 664nm,


9

originating from the 4F9/2 to 6H15/2, 6H13/2 and 6H11/2 transitions. All compounds can be efficiently

excited in the range from 250 to 350 nm. The emission intensity is much weaker for 2 and 5

compared to 4, and a broad emission band can be observed in 2 and 5 besides the 4f-4f emission

lines. In Figure 10, the excitation spectrum for this broad emission band in 5 is shown upon

monitoring the emission at 600nm. The broad excitation band from 300 to 500nm is clearly

different from the excitation spectrum of the 4f-4f transitions. The origin of this broad emission

band is probably related to the ligand (see below). Figure 11 shows the decay profile for

compounds 2, 4 and 5 upon excitation at 337nm with a pulsed nitrogen laser. The decay profiles

could be fitted with three exponentials exp(-t/τi) over (almost) three orders of magnitude. The

fitted decay constants (and their relative contribution to the total luminescent output) are 0.15µs

(5%), 1.6µs (55%) and 4.9µs (40%) for 2, 0.09ms (13%), 0.31ms (44%), 0.80ms (43%) for 4,

0.15µs (8%), 0.60µs (71%), 1.8µs (21%) for 5. The displayed intensity in Figure 11 contains only

the intensity of the 4f-4f emission lines. The broad emission band in 2 and 5 (Figure 11) has a

decay time below the detection limit of the used setup (20ns). The decay for the Sm3+ (2) and Dy3+

(5) compounds is very fast as normally a decay time in the ms range is expected for the

spin-forbidden 4f-4f transition occurring in these trivalent rare earths. This shortening is indicative

of a strong influence of non-radiative decay paths, which is closely connected to the low

efficiency of the photoluminescence in these compounds (vide supra). Compound 4 (Tb3+) shows

a much brighter photoluminescence, which is reflected in the much longer decay times, almost

being in the ms range.

Compounds 3, 6 and 7 do not show 4f-4f based emission lines. For compound 3 this is not

surprising, as the emission of Gd3+ is normally found around 32000cm-1, which is readily absorbed.

For Er3+ (compound 7) no emission around 550 nm was found and it was verified that no infrared

emission around 1550nm was present either. Figure 12 shows its emission spectrum upon

excitation at 330nm, along with the emission spectrum for the ligand (which is similar to earlier

reports 21d). The emission spectrum of 7 (Er3+) bears large similarity with the one for the ligand,

albeit with much lower intensity. Around 523nm, the emission spectrum shows a characteristic dip,

corresponding to Er3+ absorption. Consequently, the Er3+ ions are optically active, but their

emission is fully quenched, at least at room temperature. Also for compound 6 (Ho3+), no typical

4f-4f emission lines are observed, which is not uncommon due to the many cross-relaxation decay


10

paths. The emission spectrum for the Ce3+ compound 1 is rather similar to the one for the ligand,

and the typical, spin-orbit split 5d-4f emission is not observed. Decay measurements on 1 showed

that all the light is emitted within 20ns after the laser pulse, which is consistent with the decay

time of the ligand (1.3ns, 21d), but not with the common decay constant for Ce3+ (tens of ns, 26).

Based on the emission spectrum and the decay behavior, it is unlikely that any Ce3+ emission

occurs in 1.

Magnetic properties

Figure 13 shows the temperature dependence of χMT (χM stands for the molar magnetic

susceptibility) for 1. These data were measured in an applied field of 1000 Oe over the

temperature range of 2–300 K. The χMT value is equal to 0.79 cm3 K mol-1 at room temperature,

which is close to the theoretical value of 0.80 cm3 K mol-1, based upon one Ce3+ ion in the 2F5/2

ground state ( g = 6/7)27. When lowering the temperature, the value of χMT decreases to 0.46 cm3

K mol-1 at 2 K. The χM-1 vs T plot above 50 K follows the Curie–Weiss law 1/χM = (T - θ)/C with C

= 0.66 cm3 K mol-1 and θ = -19.67 K. Although a negative value of θ and decreasing values of χMT

were found in 1, we could not make any conclusion about the the existence of antiferromagnetic

coupling between two Ce3+ ions.

The magnetic susceptibility of 2 was measured in the 2-300 K temperature range with an

applied magnetic field of 1000 Oe. The thermal variation of the χMT product for 2 is presented in

Figure 14. The χMT value is 0.209 cm3 K mol-1 at 300K, which is higher than the theoretical value

of 0.09 cm3 K mol-1 based upon one Sm3+ ion in the 6H5/2 ground state (g = 2/7)23. With decreasing

temperature, the χMT value rapidly declines to a minimum of 0.00135 cm3 K mol-1 at 2K in nearly

linear relation. The χM-1 vs T plot obeys the Curie–Weiss law 1/χM = (T - θ)/C with C = 15.42cm3 K

mol-1and θ = -95.82 K. The magnetic susceptibilities can be fitted based on a Hamiltonian of the

type H =-J S1.S2 for Heisenberg infinite chain mode (Fitting equation see Support Information )28.

The best fit to the magnetic susceptibilities of 2 in the whole temperature range leads to the

parameters J = - 0.00102cm-1, zj' = - 0.0001 cm-1, g = 0.286, R =1.76×10-5

(R=∑[χmol)obs-(χmol)cal]2/∑[(χmol)obs]

2 ). The negative J value indicates the presence of very weak

antiferromagnetic interactions between the adjacent Sm(III) ions.

The magnetic susceptibilities of 3 were measured in the temperature range from 2 to 300 K and


11

under 1000 Oe field, as shown in Figure 15. The χMT value is 7.80 cm3 K mol-1at 300K, which is

close to the theoretical value of 7.88 cm3 K mol-1 based upon one Gd3+ ion in the 8S7/2 ground

state(g = 2)27. By cooling, the χMT value slightly decreases until 25 K, and below 25 K, the χMT

value decreases quickly to a minimum of 6.47 cm3 K mol-1 at 2 K. The χM-1 vs T plot obeys the

Curie–Weiss law 1/χM = (T - θ)/C with C = 7.63 cm3 K mol-1 and θ = -0.45 K, as shown in Figure

16. Judging the trend of the χMT value and the negative value of θ, it is possible to can confirm the

existence of antiferromagnetic coupling between two Gd3+ ions. Taking into account the larger

value of the local interacting spin (SGd=7/2), the classical spin expression derived by Fisher to

describe the magnetic behavior of a chain with large spins applies for 3 based on Hamiltonian

Ĥ=-ΣJi.Ji+1. The temperature dependence of the magnetic susceptibility is given by the following

equation25:

Gdchainu

uSS

u

u

kT

Ngχ

βχ

−

+=+

−

+=

11

)1(11

3

22

The Langevin function µ is defined as )1(/)/)1(coth( +−+= SSJkTkTSSJu cc . The fitting

procedure for 3 leads to J= - 0.01 cm-1, with g = 1.98 (R = 6.7×10-4,

R=∑[(χmol)obs-(χmol)cal]2/∑[(χmol)obs]

2 ). The negative J value indicates the presence of very weak

antiferromagnetic interactions between the adjacent Gd(III) ions. Comparing this conclusion with

previous findings which unanimously document the existence of an antiferromagnetic coupling in

homopolynuclear gadolinium complexes 30-32, in which the coupling constants vary from -0.0057

cm-1 to -0.053cm-1.

The magnetic susceptibilities data of 4, 5, 6, 7 were measured in the temperature range from 2

to 300 K under a 1000 Oe field, and are shown in Figure 15, The χMT value is respectively 11.54

cm3 K mol-1, 14.11 cm3 K mol-1, 13.93 cm3 K mol-1 and 11.46 cm3 K mol-1at 300K, which

approaches the theoretical value of 11.82cm3 K mol-1, 14.17 cm3 K mol-1, 14.07 cm3 K mol-1 and

11.48 cm3 K mol-1, respectively based upon one Tb3+ ion in the 7F6 ground state (g = 3/2), one

Dy3+ ion in the 6H15/2 ground state (g = 4/3), one Ho3+ ion in the 5I8 ground state (g = 5/4) and one

Er3+ ion in the 4I15/2 ground state (g = 6/5)27. The trend of the temperature dependence of the χMT

(∆) curve for 4, 5, 6 and 7 are similar to the curve of 3. However, their minimum value was 7.22

cm3 K mol-1, 9.90 cm3 K mol-1, 6.85 cm3 K mol-1 and 5.74 cm3 K mol-1 respectively. The χM-1 vs T


12

plots of 4, 5, 6 and 7 obey the Curie–Weiss law 1/χM = (T - θ)/C, which are depicted in Figure 16,

corresponding to a Curie constant C = 1.16 cm3 K mol-1, 11.85 cm3 K mol-1, 14.24 cm3 K mol-1

and 8.30 cm3 K mol-1, and Weiss constant θ = - 0.31 K, - 4.40 K, - 8.29 K and -6.80 K respectively.

However, the trends of the χMT values and the negative value of θ cannot unambiguously confirm

antiferromagnetic coupling between adjacent two Tb3+/Dy3+/Ho3+/Er3+ ions. Under the influence of

the interelectronic repulsion and spin-orbit coupling, the 4f1-13 configuration of a Ln3+ ion is split

in to 2S+1LJ spectroscopic levels. Each of these states is further split into Stark sublevels by the

crystal field. The number of Stark sublevels depends on the site symmetry of the Ln3+ ions. At

room temperature, all Stark sublevels of the2S+1LJ ground state are thermally populated. As the

temperature decreases, a depopulation of these sublevels occurs and consequently χMLnT decreases.

Only judging on the negative value of θ and the decreasing trend of values of χMLnT, it is

impossible to be certain of the existence of antiferromagnetic / ferromagnetic coupling between

adjacent Ln3+ ions, except for gadolinium(III), which fn configuration is f7(L = 0, S=7/2), and the

orbital momentum is completely quenched in the ground state.

Conclusion

In summary, we have successfully constructed seven novel Ln-Ag heterometallic coordination

polymers. 1 showed a {4.82}{4.84.10} topological framework, 2-7 are the first structurally

characterized 4d-4f polymers with a (43.65.82)(46.64) topological framework, containing two-fold

interpenetration layers. The complexes 2, 4 and 5 exhibit characteristic lanthanide luminescence of

rare earth ions Sm3+, Tb3+ and Dy3+ respectively. The magnetic behavior of 3 presents typical

weak antiferromagnetic interaction with an exchange coupling constant J = - 0.01 cm-1. The

investigation of this series of polymers provides a rational synthetic strategy for the construction

of novel materials.

Acknowledgement

This work was conducted in the framework of a project sponsored by Liaoning BaiQianWan

Talents Program and the Doctor Foundation of Liaoning Province (No. 20071016), SRF for

ROCS, SEM. PFS is Postdoctoral Fellow of the Research Foundation - Flanders (FWO). FV is

indebted to Ghent University for financial support.

Supplementary material

CCDC- No. 735031 (1), 735029 (2), 735028 (3), 735030 (4), 735026 (5), 738829 (6) and 735027


13

(7) contain the supplementary crystallographic data. These data can be obtained via the Cambridge

crystallographic Data Centre [email protected] http://www.ccdc.cam.ac.uk/deposit.

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18

Table 1. Crystal Data and Structure Refinement for 1-7

1 2 3 4 5 6 7

formula C18H12AgCe

N4O10

C18H13Ag

SmN4O10.5

C18H13Ag

GdN4O10.50

C18H13AgTb

N4O10.50

C18H13Ag

DyN4O10.5

C18H13AgHo

N4O10.5

C18H13Ag

ErN4O10.50

fw 692.31 711.54 718.44 720.11 722.69 726.12 728.45

temp(K) 293(2) 293(2) 293(2) 293(2) 293(2) 293(2) 293(2)

cryst syst Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic Orthorhombic

space group Pna2(1) Pccn Pccn Pccn Pccn Pccn Pccn

a (Å) 6.9529(14) 25.363(5) 25.287(5) 25.339(5) 25.326(5) 25.370(5) 25.285(5)

b (Å) 22.109(4) 8.5955(17) 8.5525(17) 8.5112(17) 8.4517(17) 8.4884(17) 8.4759(17)

c (Å) 11.875(2) 17.822(4) 17.827(4) 17.774(4) 17.748(4) 17.806(4) 17.765(4)

β(°) 90 90 90 90 90 90 90

V (Å)3 1825.4(6) 3885.3(13) 3855.4(13) 3833.2(13) 3798.8(13) 3834.6(13) 3807.3(13)

Z 4 8 8 8 8 8 8

ρcalc （g cm-3） 2.519 2.433 2.476 2.730 2.527 2.516 2.542

µ/mm-1 3.611 4.071 4.502 4.757 5.011 5.188 5.483

F(000) 1332 2676 2752 2737 2760 2716 2784

Reflns

collected/unique

11206 3140 24405

3417

23975

3401

29972

4568

29664

4546

24212

3380

23773

3353

GOF 1.141 1.090 1.081 1.017 1.020 1.129 1.079

R1a (I>2σ(I)) 0.0204 0.0248 0.0323 0.0270 0.0364 0.0270 0.0279

wR2b 0.0204 0.0622 0.0878 0.0743 0.0884 0.0675 0.0686

oco FFFR ∑−∑= /1a

{ } 2/1222222 ])([/])([ oco

bFwFFwwR ∑−∑=


19

Table 2. Selected Bond Lengths (Ǻ) and Angle (° ) for Compounds 1-7

1

Ce(1)-O(6)

Ce(1)-O(9)

Ce(1)-O(3)#1

Ce(1)-O(7)#2

Ce(1)-O(2)

Ce(1)-O(10)

Ce(1)-O(8)#2

Ce(1)-O(5)

Ce(1)-O(1)

Ce(1)-O(4)#1

Ag(1)-N(2)#3

Ag(1)-N(3)#4

Ag(1)-O(6)

O(6)-Ce(1)-O(9)

O(6)-Ce(1)-O(3)#1

O(9)-Ce(1)-O(3)#1

O(6)-Ce(1)-O(7)#2

O(9)-Ce(1)-O(7)#2

O(3)#1-Ce(1)-O(7)#2

O(6)-Ce(1)-O(2)

O(9)-Ce(1)-O(2)

Sm(1)-O(1)

Sm(1)-O(3)

Sm(1)-O(2)#1

Sm(1)-O(7)

Sm(1)-O(4)#2

Sm(1)-O(5)#2

Sm(1)-O(6)

Sm(1)-O(6)#2

Ag(1)-N(3)

Ag(1)-N(2)#3

O(1)-Sm(1)-O(3)

O(1)-Sm(1)-O(2)#1

O(3)-Sm(1)-O(2)#1

Gd(1)-O(3)#4

Gd(1)-O(2)#4

2.522(3)

2.526(4)

2.533(3)

2.534(3)

2.536(4)

2.593(4)

2.634(3)

2.651(3)

2.752(3)

2.773(3)

2.171(4)

2.173(4)

2.545(3)

76.24(13)

78.16(11)

135.38(14)

131.31(10)

106.76(12)

66.16(11)

113.99(11)

86.32(13)

2.345(3)

2.357(3)

2.367(3)

2.371(3)

2.374(3)

2.465(3)

2.507(3)

2.591(3)

2.117(4)

2.119(4)

73.26(9)

151.34(10)

95.16(10)

2.321(4)

2.337(4)

O(3)#1-Ce(1)-O(2)

O(7)#2-Ce(1)-O(2)

O(6)-Ce(1)-O(10)

O(9)-Ce(1)-O(10)

O(3)#1-Ce(1)-O(10)

O(7)#2-Ce(1)-O(10)

O(2)-Ce(1)-O(10)

O(6)-Ce(1)-O(8)#2

O(9)-Ce(1)-O(8)#2

O(3)#1-Ce(1)-O(8)#2

O(7)#2-Ce(1)-O(8)#2

O(2)-Ce(1)-O(8)#2

O(10)-Ce(1)-O(8)#2

O(6)-Ce(1)-O(5)

O(9)-Ce(1)-O(5)

O(3)#1-Ce(1)-O(5)

O(7)#2-Ce(1)-O(5)

O(2)-Ce(1)-O(5)

O(10)-Ce(1)-O(5)

O(8)#2-Ce(1)-O(5)

2

O(1)-Sm(1)-O(7)

O(3)-Sm(1)-O(7)

O(3)-Sm(1)-O(7)

O(1)-Sm(1)-O(4)#2

O(3)-Sm(1)-O(4)#2

O(2)#1-Sm(1)-O(4)#2

O(7)-Sm(1)-O(4)#2

O(1)-Sm(1)-O(5)#2

O(3)-Sm(1)-O(5)#2

O(2)#1-Sm(1)-O(5)#2

O(7)-Sm(1)-O(5)#2

O(4)#2-Sm(1)-O5)#2

O(1)-Sm(1)-O(6)

3

O(3)#4-Gd(1)-O(7)

O(2)#4-Gd(1)-O(7)

137.79(13)

114.70(11)

72.93(12)

65.40(11)

72.45(13)

65.59(11)

148.99(13)

139.32(10)

67.34(13)

116.08(11)

50.34(11)

81.86(11)

75.82(12)

50.26(10)

69.39(12)

117.71(10)

175.78(11)

63.91(10)

113.33(12)

125.59(11)

98.44(9)

144.74(10)

75.70(10)

87.10(11)

141.98(10)

115.50(11)

68.88(10)

126.42(9)

81.73(10)

75.68(10)

126.68(10)

84.63(11)

77.27(9)

98.27(13)

144.84(14)

O(6)-Ce(1)-O(1)

O(9)-Ce(1)-O(1)

O(3)#1-Ce(1)-O(1)

O(7)#2-Ce(1)-O(1)

O(2)-Ce(1)-O(1)

O(10)-Ce(1)-O(1)

O(8)#2-Ce(1)-O(1)

O(5)-Ce(1)-O(1)

O(6)-Ce(1)-O(4)#1

O(9)-Ce(1)-O(4)#1

O(3)#1-Ce(1)-O(4)#1

O(7)#2-Ce(1)-O(4)#1

O(2)-Ce(1)-O(4)#1

O(10)-Ce(1)-O(4)#1

O(8)#2-Ce(1)-O(4)#1

O(5)-Ce(1)-O(4)#1

O(1)-Ce(1)-O(4)#1

N(2)#3-Ag(1)-N(3)#4

N(2)#3-Ag(1)-O(6)

N(3)#4-Ag(1)-O(6)

O(3)-Sm(1)-O(6)

O(2)#1-Sm(1)-O(6)

O(7)-Sm(1)-O(6)

O(4)#2-Sm(1)-O(6)

O(5)#2-Sm(1)-O(6)

O(1)-Sm(1)-O(6)#2

O(3)-Sm(1)-O(6)#2

O(2)#1-Sm(1)-O(6)#2

O(7)-Sm(1)-O(6)#2

O(4)#2-Sm(1)-O(6)#2

O(5)#2-Sm(1)-O(6)#2

O(6)-Sm(1)-O(6)#2

N(3)-Ag(1)-N(2)#3

O(2)#4-Gd(1)-O(6)

O(4)#5-Gd(1)-O(6)

148.39(10)

121.81(13)

98.64(11)

71.99(10)

49.18(11)

136.66(11)

70.56(10)

108.31(10)

76.43(11)

149.75(12)

48.68(11)

100.92(10)

93.12(11)

117.66(12)

142.54(11)

83.21(10)

78.14(9)

153.78(14)

85.88(13)

108.80(13)

73.61(9)

74.29(10)

71.12(9)

134.07(10)

138.78(10)

75.68(9)

72.00(9)

126.51(9)

140.43(9)

71.74(10)

51.49(9)

140.98(2)

169.07(14)

73.67(13)

74.23(14)


20

Gd(1)-O(4)#5

Gd(1)-O(7)

Gd(1)-O(1)#6

Gd(1)-O(5)#7

Gd(1)-O(6)#7

Gd(1)-O(6)

Ag(2)-N(1)

Ag(21)-N(3)

O(3)#4-Gd(1)-O(2)#4

O(3)#4-Gd(1)-O(4)#5

O(2)#4-Gd(1)-O(4)#5

Tb(1)-O(3) #1

Tb(1)-O(2) #1

Tb(1)-O(4)#2

Tb(1)-O(1)

Tb(1)-O(7) #1

Tb(1)-O(5)

Tb(1)-O(6) #1

Tb(1)-O(6)

Ag(1)-N(3)

Ag(1)-N(1)#3

O(3)#1-Tb(1)-O(2)#1

O(3)#1-Tb(1)-O(4)#2

O(2)#1-Tb(1)-O(4)#2

Dy(1)-O(2)#1

Dy(1)-O(3)#1

Dy(1)-O(1)

Dy(1)-O(5)

Dy(1)-O(4)#2

Dy(1)-O(8)#1

Dy(1)-O(7)

Dy(1)-O(7)#1

Ag(1)-N(3)

Ag(1)-N(2)#3

O(2)#1-Dy(1)-O(3)#1

O(2)#1-Dy(1)-O(1)

O(3)#1-Dy(1)-O(1)

Ho(1)-O(1)

Ho(1)-O(3)

Ho(1)-O(2)#1

Ho(1)-O(7)

2.345(4)

2.346(4)

2.355(4)

2.432(4)

2.576(4)

2.483(4)

2.119(5)

2.121(5)

73.74(13)

151.51(15)

94.86(14)

2.305(3)

2.311(3)

2.321(3)

2.331(3)

2.332(3)

2.422(3)

2.477(3)

2.557(3)

2.125(3)

2.132(3)

74.13(10)

151.62(10)

94.43(10)

2.277(2)

2.288(2)

2.307(2)

2.308(2)

2.312(2)

2.397(2)

2.445(2) .

2.544(2)

2.122(3)

2.126(3)

74.93(8)

152.18(8)

94.22(8)

2.283(3)

2.297(3)

2.308(3)

2.309(3)

O(4)#5-Gd(1)-O(7)

O(3)#4-Gd(1)-O(1)#6

O(2)#4-Gd(1)-O(1)#6

O(4)#5-Gd(1)-O(1)#6

O(7)-Gd(1)-O(1)#6

O(3)#4-Gd(1)-O(5)#7

O(2)#4-Gd(1)-O(5)#7

O(4)#5-Gd(1)-O(5)#7

O(7)-Gd(1)-O(5)#7

O(1)#6-Gd(1)-O(5)#7

O(3)#4-Gd(1)-O(6)

4

O(3)#1-Tb(1)-O(1)

O(2)#1-Tb(1)-O(1)

O(4)#2-Tb(1)-O(1)

O(3)#1-Tb(1)-O(7)#1

O(2)#1-Tb(1)-O(7)#1

O(4)#2-Tb(1)-O(7)#1

O(1)-Tb(1)-O(7)#1

O(3)#1-Tb(1)-O(5)

O(2)#1-Tb(1)-O(5)

O(4)#2-Tb(1)-O(5)

O(1)-Tb(1)-O(5)

O(7)#1-Tb(1)-O(5)

O(3)#1-Tb(1)-O(6)#1

5

O(2)#1-Dy(1)-O(5)

O(3)#1-Dy(1)-O(5)

O(1)-Dy(1)-O(5)

O(2)#1-Dy(1)-O(4)#2

O(3)#1-Dy(1)-O(4)#2

O(1)-Dy(1)-O(4)#2

O(5)-Dy(1)-O(4)#2

O(2)#1-Dy(1)-O(8)#1

O(3)#1-Dy(1)-O(8)#1

O(1)-Dy(1)-O(8)#1

O(5)-Dy(1)-O(8)#1

O(4)#2-Dy(1)-O(8)#1

O(2)#1-Dy(1)-O(7)

6

O(1)-Ho(1)-O(7)

O(3)-Ho(1)-O(7)

O(2)#1-Ho(1)-O(7)

O(1)-Ho(1)-O(4)#2

75.86(14)

87.61(15)

142.38(14)

114.88(15)

68.80(15)

126.86(14)

81.77(15)

75.22(14)

126.32(14)

84.11(16)

77.49(14)

86.77(11)

142.30(10)

115.63(11)

98.52(10)

144.98(10)

75.80(11)

68.76(10)

127.60(10)

82.40(10)

74.57(10)

84.28(11)

125.13(10)

77.66(10)

98.36(7)

144.96(8)

75.69(8)

86.91(8)

142.80(8)

114.85(9)

68.72(9)

127.95(8)

82.57(8)

73.16(8)

124.64(8)

83.69(8)

77.97(8)

98.26(11)

144.87(12)

76.00(12)

87.37(12)

O(7)-Gd(1)-O(6)

O(1)#6-Gd(1)-O(6)

O(5)#7-Gd(1)-O(6)

O(3)#4-Gd(1)-O(6)#7

O(2)#4-Gd(1)-O(6)#7

O(4)#5-Gd(1)-O(6)#7

O(7)-Gd(1)-O(6)#7

O(1)#6-Gd(1)-O(6)#7

O(5)#7-Gd(1)-O(6)#7

O(6)-Gd(1)-O(6)#7

N(1)-Ag(2)-N(3)

O(2)#1-Tb(1)-O(6)#1

O(4)#2-Tb(1)-O(6)#1

O(1)-Tb(1)-O(6)#1

O(7)#1-Tb(1)-O(6)#1

O(5)-Tb(1)-O(6)#1

O(3)#1-Tb(1)-O(6)

O(2)#1-Tb(1)-O(6)

O(4)#2-Tb(1)-O(6)

O(1)-Tb(1)-O(6)

O(7)#1-Tb(1)-O(6)

O(5)-Tb(1)-O(6)

O(6)#1-Tb(1)-O(6)

N(3)-Ag(1)-N(1)#3

O(3)#1-Dy(1)-O(7)

O(1)-Dy(1)-O(7)

O(5)-Dy(1)-O(7)

O(4)#2-Dy(1)-O(7)

O(8)#1-Dy(1)-O(7)

O(2)#1-Dy(1)-O(7)#1

O(3)#1-Dy(1)-O(7)#1

O(1)-Dy(1)-O(7)#1

O(5)-Dy(1)-O(7)#1

O(4)#2-Dy(1)-O(7)#1

O(8)#1-Dy(1)-O(7)#1

O(7)-Dy(1)-O(7)#1

N(3)-Ag(1)-N(2)#3

O(3)-Ho(1)-O(6)

O(2)#1-Ho(1)-O(6)

O(7)-Ho(1)-O(6)

O(4)#2-Ho(1)-O(6)

71.17(13)

134.49(14)

138.55(14)

75.75(13)

72.29(13)

126.42(13)

140.12(14)

71.55(14)

51.85(13)

141.27(3)

169.2(2)

73.33(10)

74.16(10)

134.47(10)

71.65(10)

138.34(10)

75.90(10)

71.95(10)

125.95(10)

72.00(10)

140.82(10)

52.24(10)

140.82(2)

168.60(15)

73.27(8)

74.35(8)

71.70(8)

134.78(8)

138.33(8)

75.93(8)

72.33(8)

125.81(8)

140.48(8)

71.87(8)

52.48 (8)

141.038(18)

168.36(11)

73.62(11)

74.31(11)

71.26(11)

134.81(12)


21

Ho(1)-O(4)#2

Ho(1)-O(5)#2

Ho(1)-O(6)

Ho(1)-O(6)#2

Ag(1)-N(2)#3

Ag(1)-N(3)

O(1)-Ho(1)-O(3)

O(1)-Ho(1)-O(2)#1

O(3)-Ho(1)-O(2)#1

Er(1)-O(1)

Er(1)-O(2)

Er(1)-O(3)

Er(1)-O(1)#4

Er(1)-O(6)#5

Er(1)-O(4)#3

Er(1)-O(8)#6

Er(1)-O(7)#5

Er(1)-O(7)#6

Ag(2)-N(3)

Ag(2)-N(1)

O(2)-Er(1)-O(3)

O(2)-Er(1)-O(1)#4

O(3)-Er(1)-O(1)#4

2.311(3)

2.401(3)

2.450(3)

2.559(3)

2.128(4)

2.129(4)

74.79(11)

152.24(12)

94.16(11)

2.272(3)

2.289(3)

2.299(3)

2.301(3)

2.305(3)

2.389(3)

2.438(3)

2.552(3)

2.116(4)

2.11(4)

75.14(11)

152.26(12)

93.87(12)

O(3)-Ho(1)-O(4)#2

O(2)#1-Ho(1)-O(4)#2

O(7)-Ho(1)-O(4)#2

O(1)-Ho(1)-O(5)#2

O(3)-Ho(1)-O(5)#2

O(2)#1-Ho(1)-O(5)#2

O(7)-Ho(1)-O(5)#2

O(4)#2-Ho(1)-O(5)#2

O(1)-Ho(1)-O(6)

7

O(2)-Er(1)-O(6)#5

O(3)-Er(1)-O(6)#5

O(1)#4-Er(1)-O(6)#5

O(2)-Er(1)-O(4)#3

O(3)-Er(1)-O(4)#3

O(1)#4-Er(1)-O(4)#3

O(6)#5-Er(1)-O(4)#3

O(2)-Er(1)-O(8)#6

O(3)-Er(1)-O(8)#6

O(1)#4-Er(1)-O(8)#6

O(6)#5-Er(1)-O(8)#6

O(4)#3-Er(1)-O(8)#6

O(2)-Er(1)-O(7)#5

142.83(12)

114.57(12)

68.84(12)

127.48(11)

82.12(12)

74.29(12)

125.36(11)

83.57(13)

78.12(11)

98.22(11)

145.01(12)

76.02(12)

87.745(13)

142.98(12)

114.30(13)

68.86(12)

127.55(12)

81.78(12)

74.27(12)

125.38(11)

83.35(13)

78.12(12)

O(5)#2-Ho(1)-O(6)

O(1)-Ho(1)-O(6)#2

O(3)-Ho(1)-O(6)#2

O(2)#1-Ho(1)-O(6)#2

O(7)-Ho(1)-O(6)#2

O(4)#2-Ho(1)-O(6)#2

O(5)#2-Ho(1)-O(6)#2

O(6)-Ho(1)-O(6)#2

N(2)#3-Ag(1)-N(3)

O(3)-Er(1)-O(7)#5

O(1)#4-Er(1)-O(7)#5

O(6)#5-Er(1)-O(7)#5

O(4)#3-Er(1)-O(7)#5

O(8)#6-Er(1)-O(7)#5

O(2)-Er(1)-O(7)#6

O(3)-Er(1)-O(7)#6

O(1)#4-Er(1)-O(7)#6

O(6)#5-Er(1)-O(7)#6

O(4)#3-Er(1)-O(7)#6

O(8)#6-Er(1)-O(7)#6

O(7)#5-Er(1)-O(7)#6

N(3)-Ag(2)-N(1)

138.36(11)

75.55(10)

72.60(11)

126.09(11)

140.06(12)

71.45(11)

52.52(10)

141.43(2)

169.38(16)

73.58(11)

74.22(11)

71.43(11)

135.20(12)

138.13(12)

75.60(11)

72.89(12)

126.21(11)

139.73(12)

71.13(12)

52.60(11)

141.56(2)

169.10(16)

Symmetry transformations used to generate equivalent atoms: For 1. #1 -x+2,-y+2,z-1/2; #2 -x+1,

-y+2, z-1/2; #3 -x+3/2, y-1/2, z-1/2; #4 x-1/2, -y+3/2, z. For 2. #1 -x, y-1/2, -z+1/2; #2 -x, y+1/2,

-z+1/2; #3 x+1/2, y+1/2, -z. For 3. #4 x-1/2, y-1/2, -z+1; #5 -x+3/2, y-1, z-1/2; #6 -x+3/2, y, z-1/2;

#7 -x+1, y+1/2, -z+1/2. For 4. #1 -x, y+1/2, -z+1/2; #2 x, y+1, z; #3 x+1/2, y-1/2, -z. For 5. #1 -x,

y-1/2, -z+1/2; #2 -x, y+1/2, -z+1/2; #3 x+1/2, y+1/2, -z; #4 x-1/2, y-1/2, -z. For 6. #1 -x, y-1/2,

-z+1/2; #2 -x, y+1/2, -z+1/2; #3 x+1/2, y+1/2, -z. For 7. #3 -x+1, y+1/2, -z+1/2; #4 -x+1, y-1/2,

-z+1/2; #5 x+1/2, y+1/2, -z+1; #6 -x+1/2, y+1, z-1/2.


22

Scheme 1. Schematic representation of the observed coordination modes (a–n) of Hbidc2-. The new coordination modes described in this paper are given by modes k-n.

Figure 1. Coordination environment of Ce(III) and Ag(I) ions in 1 drawn at 30% probability level.

All hydrogen atoms are omitted for clarity. Symmetry operation codes: A=1/2-x, -1/2+y, -1/2+z;

B=1-x, -y,1/2+z.

Figure 2. One-dimensional heterometallic chain in 1.


23

Figure 3. Three-dimensional framework of 1.

Figure 4. The three-dimensional topology frameworks of 1 along the x axle, the pink balls stand

for Ce atoms, 4-connected nodes, the turquiose balls stand for Ag atoms, 3-connected nodes. The

light green balls and violet ball stand for 3-connected and 4-connected nodes respectively.


24

Figure 5. Coordination environment of Dy(III) and Ag(I) ions in 5 drawn at 30% probability level.

All hydrogen atoms and lattice water molecules are omitted for clarity. Symmetry operation codes:

A=3/2-x, y-1, z-1/2; B=-x+1, 1/2+y, 1/2-z.

Figure 6. One-dimensional Dy(COO)4

- rod substructure chain in 5.


25

Figure 7. (a) A set of 3D frameworks in 5. (b) Two sets of 3D two-fold interpenetrating

framework of 5.


26

Figure 8. The three-dimensional topology framework of 5. The pink balls represents Dy atoms,

3-connected nodes. The violet ball and turquoise ball stands for 4-connected and 5-connected

nodes respectively.

Figure 9. TGA curve of 1-7.


27

Figure 10. (Thin lines) Photoluminescence emission spectra for 2, 4 and 5 under excitation at

305nm, 315nm and 285nm, respectively. (Thick lines) Excitation spectra for the

photoluminescence in 2, 4 and 5 upon monitoring at 642nm, 545nm, 600nm (a) and 575nm (b).

Figure 11. Decay profiles for compounds 2, 4 and 5 upon excitation at 337nm. For each decay

profile, three exponential decays were fitted to the experimental data (crosses).


28

Figure 12. Photoluminescence emission for (a) the ligand, (b) compound 1 and (c) compound 7

under excitation at 330nm. The arrow indicates a Er3+ absorption.

Figure 13. Temperature dependence of the χMT(∆)and χM-1(О) curve for 1. The red line represents

the best fit of the curve.


29

Figure 14. Temperature dependence of the χMT(□)and χM

-1(○) curve for 2. The red line and green

line represent the best fit of the curve.

0 50 100 150 200 250 300

4

6

8

10

12

14

T/K

χM

T /

cm3 K

mol

-1

Gd

Tb

Dy

Ho

Er

Figure 15. Temperature dependence of the χM T curve for 3(□), 4(○), 5( ), 6( ) and 7( ). The

red lines represent the best fit of the curves for 3.


30

0 50 100 150 200 250 300

0

10

20

30

40

χM

-1 / c

m-3

mol

T/K

Gd

Tb

Dy

Ho

Er

Figure 16. Temperature dependence of the χM-1 curve for 3(□), 4(○), 5( ), 6( ), and 7( ). The red,

green, blue, wine and pink line respectively represent the best fit of the curves for 3, 4, 5 ,6 and 7.


31

Table of Contents Graphic

Seven novel 4d-4f heterometallic coordination polymers have been synthesized under

hydrothermal conditions. The X-ray structure analysis revealed that the seven complexes present

two types of three-dimensional (3D) frameworks. Polymer 1 crystallized in an orthorhombic

manner having a Pna2(1) space group, consisting of a 3D framework with a 1D heterometallic

chain. Polymers 2-7 are isostructures and all crystallized in an orthorhombic fashion having a

Pccn space group existing of a two-fold interpenetrating 3D framework. The luminescence

properties and the magnetic properties of 1 -7 were investigated.


Supporting Information (SI)

Hydrothermal synthesis, crystal structure, and properties of

Ag(I)-4f compounds based on 1H-benzimidazole - 5, 6 -

dicarboxylic acid

Ya-guang Sun, Yong-li Wu, Gang Xiong, Philippe F. Smet, Fu Ding, Mei-yan Guo, Ming-chang

Zhu, En-jun Gao, Dirk Poelman, Francis Verpoort

0 10 20 30 40 502θ / °

1 simulated

1 experimental

0 10 20 30 40 50

2 θ / °

2 s im u la te d

2 e xp e rim e n ta l

0 10 20 30 40 50

2θ / °

3 simulated

3 experimental

0 10 20 30 40 50

4 simulated

4 experimental

2θ / °

0 10 20 30 40 50

2θ / °

5 simulated

5 experimental

0 10 20 30 40 50

2θ / °

6 simulated

6 experimental


0 10 20 30 40 50

7 simulated

7 experimental

2θ / °

Fig. 1 The simulated and experimental PXRD patterns of 1-7:

Fitting equation for the magnetic susceptibilities of 2

Eq. 1:

2/55202/2782/7

66

20

55

2/27

44

8

33

2/7

2211

2

Sm876543

)()()()()(

3

2/55

xxxxx

xxxx

eeeee

ebxaebxaebxaebxaebxabxa

kTx

N x

−−−−−

−−−−

+++++

+++++++++++=

−βχ

KT

Jx =

Parameters are:

a1=2.143, b1= 7.347; a2=42.92, b2=1.641; a3=283.7, b4= 0.6571; a4=620.6, b4=1.9400; a5=1122,

b5=2.835; a6=71813, b6=3.556.

Eq. 2:

Sm

S

Ngzj χβ

χχ

)/'2(1 22

m

−=

zj' presents molecular field approximation.


Dear Editor.,

Thank you very much for your constructive suggestions for this manuscript

(DT-ART-05-2010-000579). The revision has been made according the Reviewers’

comments. Below a detailed overview of the revision is given:

a) Modifications according Reviewer 1:

1) The title has been revised, new title is " Hydrothermal synthesis, crystal structure,

and properties of Ag(I)-4f compounds based on 1H-benzimidazole -5,6-dicarboxylic

acid"

2) "excisting" has been corrected into " existing "in the section of abstract, and other

typos have been corrected.

3) We have rewritten the structural analysis, explaining the twin crystal of compound

1 in the “X-ray Crystallographic Study” section.

We have double checked the topology analysis of compound 1 very carefully and

it follows that the Ce(III) center is coordinated with ten oxygen atoms, eight

oxygen atoms derive from four carboxylate groups with chelating modes and two

oxygen atoms derive from water molecules. Therefor, the Ce(III) atom is suitable

to act as 4-connected node rather than 5-connected node. The structure was been

simplified to a 3,4-connected node net rather than 3,4,5 connected node net.

We have described compounds 2-7 with rod substructure.

4) We deleted the description of helical chain of compounds 2-7.

5) We added the discussion about the luminescence of compounds 1, 3, 6, 7 and

1H-benzimidazole-5,6-dicarboxylic acid.

6) We added the magnetic study of compound 2.

7) We discussed the magnetic property of compound 3 with 1D chain according the

reviewer’s advice.

8) We revised temperature and color of the CIF file, now they are consistent with the

manuscript.

9) We adjusted the Conclusion section, "eight" has been modified to" seven".

b) Modifications according Reviewer 2:

1) We expanded the description of the importance of interpenetration in Introduction


2）We modified the title in: "Hydrothermal synthesis, crystal structure, and properties

of Ag(I) -4f compounds based on 1H-benzimidazole -5,6-dicarboxylic acid"

3) The symmetry operation codes of Figures 1 and 5 have been given.

4) The PXRD and corresponding simulated patterns for compounds 1-7 have been

given in Supporting Information.

5) The syntax errors and the form of cited references have been adjusted.

c) Modifications according Reviewer 3:

The CIF files of Compounds 1-7 have been refined.

Finally, I and my co-workers would like to thank you for the nice cooperation

Sincerely yours,

Yaguang Sun


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