Solvated lanthanide cationic template strategy for constructing

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Solvated lanthanide cationic template strategy for constructing iodoargentates with photoluminescence and white light emission Di Zhang, Zhen-Zhen Xue, Jie Pan, Meng-Meng Shang, Ying Mu, Song-De Han, and Guo-Ming Wang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01207 • Publication Date (Web): 18 Sep 2018 Downloaded from http://pubs.acs.org on September 18, 2018

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Crystal Growth & Design

Solvated lanthanide cationic template strategy for constructing iodoargentates with photoluminescence and white light emission

Di Zhang,† Zhen-Zhen Xue,† Jie Pan,† Meng-Meng Shang,† Ying Mu, † Song-De Han, † Guo-Ming Wang*,† †

College of Chemistry and Chemical Engineering, Qingdao University, Shandong 266071, China

Supporting Information ABSTRACT: With lanthanide (Ln) cations acting as templates, a series of iodoargentates were successfully constructed, {[Ln(H2O)8][Ag8I11]}n [Ln = Eu3+ (1-Eu), Tb3+ (1-Tb)], {[Ln(DMF)8][Ag6I9]}n [Ln = Eu3+ (2-Eu), Tm3+ (2-Tm), DMF = N, Ndimethylformamide], {[Ln(H2O)8[Ag15I18]}n [Ln = Eu3+ (3-Eu), Tb3+ (3-Tb)]. The iodoargentates feature special luminescent performance through the introduction of Ln3+ ions, which is demonstrated by corresponding Eu, Tb, Tm-based compounds exhibiting characteristic emission bands as well as distinctive emission colors. Moreover, the iodoargentate with doped Ln cations {[Eu0.531Tb0.117Tm0.352(DMF)8][Ag6I9]}n (2-Eu0.531Tb0.117Tm0.352) was finally obtained, displaying a white light emission under UV excitation at room temperature.

Introduction Metal halides have attracted much interest currently owing to their abundant architectures and potential applications in catalysis, photoluminescence, semiconductor, etc.1-8 Among them, numerous iodocuprates and iodoargentates have been constructed by virtue of the flexible coordination mode of Iions (from µ2- to µ8-bridiging) as well as Cu+/Ag+ ions (linear, triangular and tetrahedral).9-12 To obtain these promising iodometallates, the template-directed synthesis strategy has been widely used. Commonly, there are three kinds of template according to their intrinsic nature. The organic template, especially organoamines, is the most famous one, and the intensively studied halometallates bearing perovskite structure which have witnessed extraordinary breakthroughs in photovoltaics are the representative of such compounds.13-15 Inorganic template is another one, such as alkali metals, through which various iodometallates have been successfully synthesized.16,17 The third one, called organic-inorganic hybrid, has been well demonstrated by the in situ generated metal-organic complexes to direct the assembly.18-20 For instance, two iodoargentates, M(en)3Ag2I4 (M= Mn2+ and Mg2+; en = ethylenediamine) were prepared by Ren’s group, in which the structures could be subtly modulated by metal coordination cations.21 Generally speaking, the effectiveness of these kinds of template to fabricate iodometallates has been confirmed in recent publications. Meanwhile, the inorganic templates are relatively less compared with the flourishing development of the others, greatly limiting the assembly of corresponding products. Lanthanide (Ln) ions, usually displaying the special optical features such as highly monochromatic emissions and long lifetimes, have been widely utilized in the areas of display devices and biomedical analysis.22-25 The luminescent

emission band of Ln-based complexes can span over the entire spectrum including ultraviolet, visible and near-infrared region, thus leading to the easy acquisition of numerous of photoactive materials with various luminescent colors. For example, incorporating Sm3+, Eu3+ and Tb3+ into the structural spaces of bio-MOF-1 by post-synthetic ion exchange process, An et al successfully synthesized the Ln3+@bio-MOF-1 with their distinctive emission colors (Sm3+, orange-pink; Eu3+, red; Tb3+, Green).26 Moreover, a combination of red, green and blue emitter into one framework can generate functional materials with white light emission luminescence, which shows promising applications in lighting and display. Codoping of IFP-1 with photoactive Eu3+ and Tb3+ ions provides a great possibility to turn the primary emission color to the white, which was systematically investigated by Holdt’s work.27 Hong reported a doped Ln coordination polymer with emission of white light by accurately regulating the proportion of Eu3+ and Tb3+ in the Gd3+ analog. The combination of blue light from the emission of ligand with the intense emissions of Eu3+ and Tb3+ centers presents an effective way to accomplish the task.28 Based on the above considerations, we attempt to explore the iodometallates with lanthanide cation templates in this work taking into account the following thoughts: (a) the lanthanide cations can not only balance the negative charge of the inorganic moieties but also result in iodometallates with diverse architectures; (b) the introduction of Ln3+ ions can endow the iodometallates with special luminescent performance; (c) iodometallates with doped Ln cations could exhibit white light emission at ambient temperature. As a result, a series of iodoargentates templated by lanthanide cations was constructed, {[Ln(H2O)8][Ag8I11]}n [Ln = Eu3+ (1Eu), Tb3+ (1-Tb)], {[Ln(DMF)8][Ag6I9]}n [Ln = Eu3+ (2-Eu), Tm3+ (2-Tm), DMF = N, N-dimethylformamide], {[Ln(H2O)8[Ag15I18]}n [Ln = Eu3+ (3-Eu), Tb3+ (3-Tb)]. The

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photoluminescent properties of all the compounds have been investigated in detail. Moreover, the iodoargentates with doped lanthanide ions based on compounds 2-Eu and 2-Tm, {[Eu0.531Tb0.117Tm0.352(DMF)8][Ag6I9]}n (2Eu0.531Tb0.117Tm0.352) was successfully obtained, displaying the white light emission under UV excitation at ambient temperature.

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Then 0.1 mL HI (45 wt%) was dropwise added into the mixture. After stirring 2 hours, the filtrate was evaporated at ambient temperature. Colorless crystals were formed after 5 days. Synthesis of {[Ln(DMF)8][Ag6I9]}n. [Ln = Eu3+ (2-Eu), Tm3+ (2-Tm)]. The syntheses of 2-Eu and 2-Tm were similar to that of 1-Eu and 1-Tb, but DMSO was replaced by DMF. After 3 days, colorless block crystals were harvested. Synthesis of {[Ln(H2O)8[Ag15I18]}n [Ln = Eu3+ (3-Eu), Tb3+ (3-Tb)]. The synthesis of 3-Eu and 3-Tb were similar to that of 1-Eu and 1-Tb, respectively, but DMSO was replaced by NMP (NMP = N-Methyl pyrrolidone). Colorless block crystals were obtained after 7 days. Synthesis of {[Eu0.531Tb0.117Tm0.352(DMF)8][Ag6I9]}n (2Eu0.531Tb0.117Tm0.352). A mixture of 47 mg AgI, 40 mg Eu(NO3)3·6H2O, 7 mg Tb(NO3)3·6H2O and 37 mg Tm(NO3)3·6H2O was dissolved in 2 mL DMF, 8 mL CH3CN and 0.1 mL HI (45 wt%). The content was stirred for 2 hours, and the filtrate was permitted to evaporate. Colorless block crystals were formed after 3 days.

Experimental Section Chemical reagents used in our work are commercially obtainable without purification. Detailed information about Xray crystallography and physical measurements are summarized in Supporting Information. CCDC 1842171, 1853306, 1842172, 1853307, 1853308, 1853309 contains the supplementary crystallographic data for 1-Eu/Tb, 2-Eu/Tm and 3-Eu/Tb in this paper, respectively. The detailed crystallographic data together with structure determination summaries for the six compounds are listed in Table 1. Synthesis of {[Ln(H2O)8][Ag8I11]}n. [Ln = Eu3+ (1-Eu), Tb3+ (1-Tb)]. 47 mg AgI and 90 mg Ln(NO3)3·6H2O were added to a 10 mL dimethyl sulfoxide (DMSO)-CH3CN (1:4) solution.

Table 1 Crystal data and refinement details for the compounds. Compound Empirical formula

1-Eu

1-Tb

2-Eu

2-Tm

3-Eu

3-Tb

H16O8Ag8I11Eu

H16O8Ag8I11Tb

C24H56N8O8Ag6I9Eu

C24H56N8O8Ag6I9Tm

H2.66O1.33Ag2.5I3Eu0.17

H2.66O1.33Ag2.5I3Tb0.17

Formula weight

2554.98

2561.94

2526.06

2543.03

700.18

701.36

Crystal system

Orthorhombic

Orthorhombic

Monoclinic

Monoclinic

Orthorhombic

Orthorhombic

Pbcm

Pbcm

C2/c

C2/c

Ibam

Ibam

a (Å)

Space group

11.4308 (7)

11.3950 (4)

20.540 (3)

20.643 (2)

28.416 (3)

28.442 (2)

b (Å)

22.8130 (9)

22.8273 (11)

18.4374 (16)

18.4729 (12)

8.0006 (6)

7.9857 (6)

c (Å)

50.361 (2)

50.4731 (19)

16.890 (2)

16.8800 (15)

27.296 (3)

27.292 (2)

α (o)

90.00

90.00

90.00

90.00

90.00

90.00

β()

90.00

90.00

114.548 (15)

114.447(10)

90.00

90.00

γ (o)

90.00

90.00

90.00

90.00

90.00

90.00

13132.7 (11)

13128.9(9)

5818.2 (13)

5859.7(9)

6205.7(10)

6198.8(9)

8

8

4

4

16

16

o

3

V (Å ) Z 3

Dc (g/cm )

2.568

2.576

2.884

2.883

2.893

2.901

µ (mm-1)

8.453

8.578

7.855

8.243

9.710

9.807

2.6–21.7

2.6-20.1

2.7–24.5

2.7-24.8

2.7-22.9

2.7-23.0

0.0645, 0.1840

0.0846, 0.2676

0.0518, 0.1379

0.0474, 0.1020

0.0613, 0.2103

0.0597, 0.1952

0.822

1.061

1.102

0.999

1.008

0.890

θ range (°) a

b

R1, wR2 (I >2σ( I)) GOF on F2 a

b

R = Σ(||Fo| - |Fc||)/Σ|Fo|. Rw =

{[Σw[(Fo2

-

Fc2)2/Σw(Fo2)2]}1/2.

structural analysis, 1-Eu belongs to an orthorhombic Pbcm space group, exhibiting an interesting two-dimensional (2D) structure. The crystallographically asymmetric unit is composed of eight Ag(I) ions, eleven iodide ions, a couple of half Eu(III) ions and eight coordinated water molecules. In 1Eu, Ag(I) centers are located in two different kinds of coordination environment as clearly depicted in Fig. 1a. Ag1, Ag2, and Ag4-Ag8 ions are linked by four I- centers with {AgI4} tetrahedral geometry, while Ag3 adopts a {AgI3} triangle coordination environment. Similarly, diverse coordination environments are also observed for iodide ions, such as µ2- (I1, I3, I7, I11), µ3- (I2, I4, I6, I8, I10) and µ4- (I5, I9) bridging modes.

Results and Discussion Reaction and evaporation of AgI with Ln(NO3)3·6H2O in different mixed solvents afforded a series of iodoargentates templated by lanthanide cations. Structural analyses indicate that the various solvents can act as an important effect in the structural control during self-assembly process, which gives rise to a possibility in generating novel iodoargentates with diverse network structures. Crystal Structure of {[Ln(H2O)8][Ag8I11]}n. [Ln = Eu3+ (1Eu), Tb3+ (1-Tb)]. Compounds 1-Eu and 1-Tb are isomorphous (Fig. S1), thus we employ 1-Eu as a representative and discuss it in detail. According to the

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accompanied with the linkage with four iodide ions. That is, Ag1 connecting to one µ3-I, one µ4-I and two µ2-I, Ag2 being bridged by one µ2-I, one µ4-I and two µ3-I, Ag3 linking to two µ2-I and two µ4-I centers. In 2-Eu, the distances of Ag-I bond vary between 2.77 and 3.01 Å, and I-Ag-I angles are in 95.9124.4°. Notably, the distance of Ag1-Ag2 (3.052 Å) and Ag1Ag3 (3.368 Å) indicates the existence of argentophilic interactions, whose lengths are in the range of 2.88 Å (distance of metallic silver) to 3.44 Å (van der Waals radius sum of silver). The Eu(III) ion is coordinated by eight DMF molecules and adopts a square antiprismatic environment to generate a [Eu(DMF)8]3+ entity with bond lengths between Eu and O being in 2.26-2.41 Å. Noteworthily, the tetrahedral [AgI4] subunit undergoes a variety of self-condensations to generate a [Ag6I12] fragment. Furthermore, the neighboring [Ag6I12] fragments share peripheral iodide ions to construct a 1D [Ag6I9] inorganic anionic chain in ab plane (Fig. 2b). The neighboring [Ag6I9] chains are parallel to each other along a- and b-axes, resulting in the 3D supramolecular structure (Fig. 2c and 2d). The cationic [Eu(H2O)8]3+ templates are dispersed among the space of anionic chains acting as charge-balancing agents.

Fig. 1 (a) Coordination modes for different centers; (b) The window with 18-membered ring and [Ag8I14] building unit; (c) 2D structure along [001] direction; (d) 3D architecture of 1-Eu.

One AgI3 triangle and seven AgI4 tetrahedrons share edges and faces to form a [Ag8I14] building unit, which features an original structural moiety in the field of Ag-I-based clusters (Fig. 1b). As depicted in Fig. 1c, adjacent [Ag8I14] units are further connected into a 2D [Ag8I11] anionic layer by sharing µ2-I1 and µ2-I7 ions. Resultantly, a 2D layer containing a [Ag9I9] window with the size of 10.176 × 11.431 Å2 is formed along c-axis. Interestingly, there are two isolated [Eu(H2O)8]3+ cations in the structure of 1-Eu. Both Eu1 and Eu2 are defined by eight coordinated water molecules and display distorted square antiprismatic geometries, with bond lengths of Eu-O being in 2.24-2.28 Å for Eu1 and 2.30-2.37 Å for Eu2, respectively. Moreover, adjacent layers adopt a paralleled configuration (−AAA– sequence) along [001] orientation, further stacking into a 3D supramolecular structure (Fig. 1d) with [Eu(H2O)8]3+ cations occupying the 18-membered windows as charge balance and space filling agents. With the help of program PLATON, we can be informed that these extra-framework [Eu(H2O)8]3+ cations occupy 62.8% of the unit cell volume. Unlike numerous reported iodoargentates directed by organic amines, such as [HCP][Ag2I3],29 [H3(Dabco)2][Ag3I6]30 and [N-Bz-Py]4[Ag9I13],31 compound 1-Eu is a 2D anionic structure directed by inorganic [Ln(H2O)8] cations. Though a 2D [Ag2I5][Ag5I8] layer directed by [Tb(DMSO)8] has been reported by Daniele and co-workers,32 the [Ag8I14] building block in 1-Eu exhibits a new structural motif among all the well-known Ag-I clusters. Especially, the 2D [Ag8I11]n reported here on the basis of [Ag8I14] units presents a novel microporous layer with a large pore size in hybrid iodoargentate system.

Fig. 2 (a) Coordination modes of the Ag(I) and Eu(III) ions; (b) The 1D [Ag6I9] chain; (c) and (d) View of 3D supermolecular structure from different directions

Crystal Structure of {[Ln(H2O)8[Ag15I18]}n [Ln = Eu3+ (3Eu), Tb3+ (3-Tb)]. If the solvent was changed to NMP in the preparation of iodoargentates, compounds 3-Eu and 3-Tb could be harvested. 3-Eu is discussed in detail as a representative due to the isostructural architecture between the two compounds according to the X-ray diffraction analyses (Fig. S3). Compound 3-Eu is in orthorhombic system Ibam space group with two and a half Ag(I) ions, three iodide ions and one-sixth uncoordinated Eu(III) ion residing in the asymmetry unit (Fig. 3a). Each Ag(I) is bridged to one µ5-I and three µ3-I ions with a distorted tetrahedral geometry. Interestingly, a novel quasi-pentagram [Ag5I6] cluster is formed with five µ3- and one µ5-bridging iodide ions linking five Ag(I) cations (Fig. 3b). The distance of Ag···Ag in 3.2143.258 Å indicates that strong metal-metal interactions exist in 3-Eu. As shown in Fig. 3c, neighboring [Ag5I6] building units are further interconnected via µ3-I-Ag bonds to form the 1D

Crystal Structure of {[Ln(DMF)8][Ag6I9]}n. [Ln = Eu3+ (2Eu), Tm3+ (2-Tm)]. When DMF was used instead of DMSO in the synthesis process, compounds 2-Eu and 2-Tm were obtained. They are isostructural (Fig. S2), so compound 2-Eu is discussed as a representative. 2-Eu belongs to monoclinic system and C2/c space group, with three Ag(I) ions, four and a half iodide ions, half of a Eu(III) ion and four coordinated DMF solvent molecules being in asymmetric unit. We can see from Fig. 2a that each Ag(I) adopt a tetrahedral geometry



[Ag5I6]- spider-web shaped anionic chain along b-axis. The space among anionic chains are occupied by [Eu(H2O)8]3+ cations. Notably, the 1D [Ag5I6] chain directed by Ln3+ cations has not been characterized until now. Adjacent inorganic chains are further held together by electrostatic interaction between the Eu(III) cations and the Ag-I based anionic chains, generating an intricate supramolecular structure. (Fig. 3d).

Fig. 3 (a) Coordination modes observed in Ag(I); (b) [Ag5I6] building block; (c) 1D spider-web shaped chain structure; (d) View of the supermolecule of 3-Eu.

Photoluminescence Properties. Lanthanide-based compounds are potential luminescent materials as light emitting devices as well as chemical sensors. Hence, solidstate luminescence behavior of representative lanthanidebased metal halides has been investigated. Being excitated at 395 nm (Fig. S4), 1-Eu, 2-Eu and 3-Eu show similar characteristic red emissions, and display slightly different peaks at 593, 615, 651, 698 nm for 1-Eu, 591, 614, 650, 698 nm for 2-Eu, and 592, 612, 650, 698 nm for 3-Eu, respectively. These four characteristic bands can be ascribed to transitions from excited state 5D0 to ground state multiplet 7 F0, 1, 2, 3, 4 (Fig. 4a).33-35 For terbium compounds, emission peaks at 488, 544, 586 and 619 nm are observed for both 1-Tb and 3-Tb (Fig. 4b), corresponding to transitions of the metal center from 5D4 to 7FJ (J = 6−3) under excitation at 370 nm (Fig. S5).36,37 Through monitoring the maximum emission of Eu and Tb-based compounds, time-resolved luminescence was further investigated, and their fitted decay curves with a single exponential function were displayed in Fig. 5. The luminescent lifetimes are found to be τ1-Eu = 1.17, τ2-Eu = 0.41, τ3-Eu = 0.21, τ1-Tb = 1.84, τ3-Tb = 1.38 ms, respectively. Comparing with the Tb-based compounds, the relatively shorter luminescent lifetimes for corresponding Eu-based compounds are due to their smaller energy gaps for Eu(III) center, which are quenched more efficiently through nonradiative deactivation process.38,39

Fig.4 (a) Emission spectra of Eu-based compounds; (b) Emission spectra of Tb-based compounds.

Fig.5 Luminescent decay curves for different compounds.


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region as shown in Fig. 6, wherein narrow emission band at 455 nm comes from Tm3+ (blue), 490 nm and 546 nm are from Tb3+ (green) and the peaks centered at 593 nm and 614 nm are due to Eu3+ (red). Notably, under UV-light irradiation, 2Eu0.531Tb0.117Tm0.352 shows a strong white luminescence and can be easily surveyed by naked eye, as clearly displayed in the inset of Fig. 6a. Based on the above results, we can observe that the red emission of the Eu(III) ions, together with green and blue emissions of doped Tb(III) and Tm(III) ions occur simultaneously. As a result, a white light emission is accomplished. The present investigation highlights that the white light emission based on metal halides with doped Ln(III) ions is entirely feasible, which could provide a convenient and promising strategy to the acquisition of unique white-lightemitting materials.

Conclusions In summary, a series of iodoargentate architectures incorporating solvated lanthanide cationic templates and exhibiting tunable luminescent properties were synthesized. The diverse structure with different dimensions in iodoargentates could be attributed to the different solvent molecules that are employed in the synthesis process (1, DMSO; 2, DMF; 3, NMP). Interestingly, the participation of rare earth ions in metal-halides system endows these materials with good luminescence performance. Moreover, the iodoargentate with doped solvated Ln cations in this work displays a white light emission, which is firstly realized in iodometallates, providing a novel and promising approach to design and prepare white-light-emitting solids.

ASSOCIATED CONTENT Supporting Information. Crystal data and refinement details, PXRD, TGA and additional figures. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author

Fig.6 (a) Emission spectra of 2-Eu0.531Tb0.117Tm0.352; (b) CIE chromaticity diagram of 2-Eu0.531Tb0.117Tm0.352.

*E-mail: [email protected]. Notes

Compounds 2-Eu and 2-Tm, emitting the primary colors (red and blue), urges us to acquire a white luminescent material. They were selected as representatives among the six compounds owing to their relatively high luminescence performance as well as good stabilities (Fig. S6). As we know, generation of the white light could be accomplished as appropriate incorporation of diverse lanthanide ions into one sample with a proper percentage.40-43 For compound 2-Eu, if red emission color with Eu(III) is further combined with green and blue emission that from the contribution of Tb(III)32 and Tm(III) (typical blue emission in visible region) ions (Fig. S7S9), photoluminescent emission with white light could be realized. As expected, the mixed lanthanide (Eu3+, Tb3+, Tm3+) iodoargentate, {[Eu0.531Tb0.117Tm0.352(DMF)8][Ag6I9]}n (2Eu0.531Tb0.117Tm0.352) with 53.1 mol% Eu(III), 11.7 mol% Tb(III) and 35.2 mol% Tm(III) was successfully synthesized and further confirmed by ICP through precisely adjusting the percentage of doped ions, which could emit white-tunable light. Upon exciting at 370 nm, the emission spectrum of 2Eu0.531Tb0.117Tm0.352 covers almost the whole visible spectral

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS We are thankful to the support from National Natural Science Foundation of China (21571111, 21601100), and Natural Science Foundation of Shandong Province (ZR2016BP02).

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For Table of Contents Use Only

Manuscript title: Solvated lanthanide cationic template strategy for constructing iodoargentates with photoluminescence and white light emission Author list: Di Zhang, Zhen-Zhen Xue, Jie Pan, Meng-Meng Shang, Ying Mu, Song-De Han, GuoMing Wang*

Synopsis: A series of iodoargentates templated by solvated lanthanide complex cations were successfully synthesized featuring photoluminescence and white light emission.


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Solvated lanthanide cationic template strategy for constructing

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