New Layered Metal Phosphonates Based on Functionalized

Article pubs.acs.org/crystal

New Layered Metal Phosphonates Based on Functionalized Phosphonic Acids Ruibiao Fu,* Shengmin Hu, and Xintao Wu State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian 350002, China S Supporting Information *

ABSTRACT: Hydrothermal reactions of ZnII or MnII ion with 1-C10H7CH2N(CH2COOH)(CH2PO3H2)(H3L1), 3-HOOC-C6H4-CH2N(CH2COOH)(CH2PO3H2)(H4L2), and 4-HOOC-C6H4-CH2N(CH2COOH)(CH2PO3H2)(H4L3) afforded six new layered metal phosphonates, namely, [Zn3(HL1)3]· 3H2O (1), [Zn(HL1)]·CH3COOH (2), [Zn(H2L2)] (3), [Mn(H3L2)2] (4), [Mn(H3L3)2] (5), and [Zn(H2L3)]·H2O (6). Compounds 1−6 are characterized by single-crystal X-ray diffraction (XRD), powder XRD, IR spectroscopy, elemental analysis, and thermogravimetric analysis (TGA). In compounds 1−3 and 6, each [ZnO4] tetrahedron shares three corners with three neighboring [PCO3] tetrahedra to generate a Zn−O−P layer, which consists of eight and four member rings (MRs). While in compounds 4 and 5, each [MnO6] octahedron shares four corners with neighboring four [PCO3] tetrahedra into a Mn−O−P layer containing eight MRs. The organic groups hang on two sides of a Zn−O−P or Mn−O−P layer to form two-dimensional (2D) sandwich-like frameworks of compounds 1−6. TGA and powder XRD reveal that 2D frameworks of compounds 2, 3, 4, and 6 are thermally stable up to 180, 250, 230, and 250 °C under an air atmosphere, respectively. It is interesting that compounds 1−2 display bright UV luminescence, which can be irreversibly quenched by UV irradiation. In addition, the blue luminescence of solid 6 can be transformed into blue-green emission by simply a heating treatment.

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INTRODUCTION The study of metal phosphonates is an ongoing field of research, due to their structural diversities and potential applications as porous materials, ion-exchangers, proton conductors, Langmuir−Blodgett Films, nonlinear optics, molecular sensors, catalysts, magnets, and so on.1−3 The phosphonate group has three oxygen atoms that can take part in coordination with metal ions, resulting in the low solubility of metal phosphonates in nature. During the last four years, much effort has been devoted to modify phosphonic acids with additional groups, including amino, carboxylate, thienyl, pyridyl, hydroxyl, triazole, imidazole, piperidine, pyrazine, and thiophene.4−13 As a result, many intriguing metal phosphonates have been obtained and structurally characterized, such as calcium phosphonates with tuned proton conductivity.4a In this regard, we have recently focused on our attention on the synthesis of functionalized phosphonic acids by the combination of the N(CH2COOH)(CH2PO3H2) moiety and other organic groups. On the basis of these functionalized phosphonate ligands, 12 luminescent metal phosphonates with three-dimensional (3D) frameworks, hybrid layers, or polynuclear clusters, have been obtained under hydrothermal conditions.14 In order to explore new luminescent metal phosphonates based on 1-C 10 H 7 -CH 2 N(CH 2 COOH)(CH2PO3H2) (H3L1; Scheme 1), many experiments have been continuously performed under different reaction con© XXXX American Chemical Society

ditions. On the other hand, 4-HOOCC6H4CH2NCH2PO3H2)2 has been proven to be an useful ligand for the formation of metal phosphonates with different frameworks.15 For instance, layered [Cd3(H 2O)3(4-HOOCC6H4CH2NH(CH2PO3)2)]· 11H2O can be reversibly dehydrated−hydrated, and intercalated additional water molecules after mechanical stress and grinding in the presence of water.15c Inspired by the above results, two new functionalized phosphonic acids, 3-HOOCC 6 H 4 -CH 2 N(CH 2 COOH)(CH 2 PO 3 H 2 ) (H 4 L2) and 4HOOC-C6H4-CH2N(CH2COOH)(CH2PO3H2) (H4L3), featuring a connection of phosphonate, carboxylate, and benzoate groups via N(CH2)3 moiety, have been successfully synthesized. Such new multifunctional phosphonate ligands would adopt diversified coordination modes to form many interesting metal phosphonates. Herein, we report synthesis, structures, thermal stabilities, and luminescence of six new layered metal phosphonates: [Zn 3 (HL1) 3 ]·3H 2 O (1), [Zn(HL1)]· CH3COOH (2), [Zn(H2L2)] (3), [Mn(H3L2)2] (4), [Mn(H3L3)2] (5), and [Zn(H2L3)]·H2O (6). Received: March 27, 2015 Revised: April 28, 2015

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DOI: 10.1021/acs.cgd.5b00423 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

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Scheme 1. Structures of H3L1 (Left), H4L2 (Middle) and H4L3 (Right)

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1328w, 1258w, 1161m(υPO), 1112s(υP−O), 1049m(υP−O), 1039m(υP−O), 1005w, 988w, 932w, 835w, 801m, 776m, 734w, 596w, 520w. Synthesis of [Zn(H2L2)] (3). A mixture of Zn(CH3COO)2·2H2O (0.1202 g, 0.5481 mmol) and H4L2 (0.0638 g, 0.211 mmol) in 8.0 mL of distilled water with the pH value adjusted to 1.67 was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 120 °C for 12 h. After slow cooling to room temperature, colorless prism-like crystals of 3 were obtained as a homogeneous phase based on powder XRD patterns. Yield: 0.0132 g (17%). Anal. Calc. for C11H12NO7PZn: C 36.04, H 3.30, N 3.82%. Found: C 36.42, H 3.32, N 3.69%. IR (KBr pellet, cm−1): 3007w, 2960w(υC−H), 2920w(υC−H), 2859w(υC−H), 2766w, 1699s(υasCO), 1638m, 1508w, 1429w, 1398w, 1385m, 1327w, 1200w, 1165w(υPO), 1117s(υP−O), 1067w, 1040m(υP−O), 1007w, 924w, 820w, 773w, 746w, 727w, 696w, 594w. Synthesis of [Mn(H3L2)2] (4). A mixture of Mn(CH3COO)2· 4H2O (0.1501 g, 0.6124 mmol) and H4L2 (0.0634 g, 0.209 mmol) in 6.0 mL of distilled water with the pH value adjusted to 2.01 was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 120 °C for 12 h. After slow cooling to room temperature, colorless prism-like crystals of 4 were obtained as a homogeneous phase based on powder XRD patterns. Yield: 0.0211 g (15%). Anal. Calc. for C22H26N2O14P2Mn: C 40.08, H 3.97, N 4.25%. Found: C 39.81, H 4.02, N 4.17% IR (KBr pellet, cm−1): 3074w, 3017w, 2968w(υC−H), 2824w, 2679w, 2567w, 1697s(υasCO), 1653w, 1636w, 1611w, 1587w, 1576w, 1558m, 1541m, 1522w, 1508w, 1458m, 1418s, 1387m, 1360w, 1337w, 1263w, 1207w, 1194m, 1175s(υPO), 1105s(υP−O), 1003m(υP−O), 951m, 922m, 831w, 808w, 772s, 747m, 694m, 571m, 513s. Synthesis of [Mn(H3L3)2] (5). A mixture of Mn(CH3COO)2· 4H2O (0.1559 g, 0.6361 mmol), H4L3 (0.0625 g, 0.206 mmol) in 6.0 mL of distilled water with the pH value adjusted to 1.98 was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 120 °C for 12 h. After slow cooling to room temperature, colorless prism-like crystals of 5 were obtained as a homogeneous phase based on powder XRD patterns. Yield: 0.0027 g (2%). Anal. Calc. for C22H26N2O14P2Mn: C 40.08, H 3.97, N 4.25%. Found: C 40.00, H 4.15, N 4.18%. IR (KBr pellet, cm−1): 3065w, 2920w(υC−H), 2852w(υC−H), 2775w, 2673w, 1701s(υasCO), 1686w, 1653w, 1616w, 1578w, 1558w, 1541w, 1522w, 1508w, 1456m, 1423s, 1387m, 1362w, 1339w, 1292w, 1240w, 1188m, 1171s(υPO), 1105s(υP−O), 1001m(υP−O), 952m, 878m, 812w, 772s, 746m, 696m, 575m, 509s. Synthesis of [Zn(H2L3)]·H2O (6). A mixture of Zn(CH3COO)2· 2H2O (0.0241 g, 0.110 mmol) and H4L3 (0.0631g, 0.208 mmol) in 6.0 mL of distilled water with the pH value adjusted to 2.39 was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 120 °C for 12 h. After slow cooling to room temperature, colorless prism-like crystals of 6 were obtained as a homogeneous phase based on powder XRD patterns. Yield: 0.0101 g (24%). Anal. Calc. for C11H14NO8PZn: C 34.35, H 3.67, N 3.64%. Found: C 34.00, H 3.75, N 3.66%. IR (KBr pellet, cm−1): 3028w, 3001w, 2963w(υC−H), 2922w(υC−H), 2853w(υC−H), 2789w, 1701s(υasCO), 1616m, 1578w, 1558w, 1541w, 1508w, 1408m, 1362w, 1317w, 1265w, 1194w, 1165w(υPO), 1109s(υP−O), 1036m(υP−O), 953w, 924w, 893w, 872w, 810w, 787m, 770w, 745m, 704m, 602m, 554w, 505m. Heating Treatment. Solids 2-180, 3-250, 4-230, and 6-250 were obtained after polycrystalline of 2, 3, 4, and 6 were heated at 180, 250, 230, and 250 °C under an air atmosphere for 2 h, respectively, and then naturally cooled to room temperature. X-ray Crystallography. X-ray data for compounds 1−6 were collected at 293(2) K on a Rigaku Mercury CCD/AFC diffractometer

EXPERIMENTAL SECTION

General. H3L1 was prepared by N-alkylation reaction according to the reported procedure.14d Other reagents were obtained from commercial sources without further purification. Elemental analyses were carried out with a Vario EL III element analyzer. Infrared spectra were obtained on a VERTEX 70 FT-IR spectrometer. The emission and excitation spectra were performed in solid state at room temperature with a F-7000 FL spectrophotometer, while the lifetime was investigated in the solid state with an Edinburgh FLS920 fluorescence spectrometer. Thermogravimetric analysis (TGA) was performed on a Netzsch STA449C at a heating rate of 10 °C·min−1 from room temperature to 1000 °C under an air (for 1−2 and 5−6) and a nitrogen (for 3−4) gas flow. Powder X-ray diffraction (XRD) patterns were acquired on a DMAX-2500 diffractometer and a MiniFlex II diffractometer using Cu−Kα radiation under ambient environment. Synthesis of 3-HOOC-C6H4-CH2N(CH2COOH)(CH2 PO3H2) (H 4 L2). A solution of glyphosate (18.6 g, 110 mmol), 3(chloromethyl)benzoic acid (17.0 g, 100 mmol), K2CO3 (76.8 g, 550 mmol), and KI (9.9 g, 60 mmol) in 500 mL of distilled water was refluxed at 90 °C under a nitrogen gas flow for 13 h. After being cooled to room temperature, the solution was acidified by concentrated hydrochloric acid to a pH value of 2.4. The desired white H4L2 was precipitated, collected by filtration, and washed with acetone. Yield: 62% (19 g) based on 3-(chloromethyl)benzoic acid. ESI-MS: calcd. mass MS m/e 302.2 [H3L2−]. Found 302.5 (100%). Synthesis of 4-HOOC-C6H4-CH2N(CH2COOH)(CH2 PO3H2) (H 4 L3). A solution of glyphosate (18.6 g, 110 mmol), 4(chloromethyl)benzoic acid (17.0 g, 100 mmol), and triethylamine (85 mL) in 500 mL of ethanol was refluxed at 90 °C under a nitrogen gas flow for 16 h. Afterward, the solvent was evaporated in vacuo, and the residue was dissolved in water. The solution was acidified by concentrated hydrochloric acid to a pH value of 2.4. The desired white H4L3 was precipitated, collected by filtration, and washed with distilled water. Yield: 79% (24 g) based on 4-(chloromethyl) benzoic acid. ESIMS: calcd. mass MS m/e 302.2 [H3L3−]. Found 302.7 (100%). Synthesis of [Zn3(HL1)3]·3H2O (1). A mixture of ZnSO4·7H2O (0.2502 g, 0.8701 mmol), H3L1 (0.0946 g, 0.306 mmol), and Na2SO4 (2.0028 g, 14.098 mmol) in 4.0 mL of distilled water with the pH value adjusted to 1.85 was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 120 °C for 12 h. After slow cooling to room temperature, colorless prism-like crystals of 1 were obtained as a homogeneous phase based on powder XRD patterns. Yield: 0.0594 g (50%). Anal. Calc. for C42H48N3O18P3Zn3: C 43.05, H 4.13, N 3.59%. Found: C 43.54, H 4.18, N 3.47%. IR (KBr pellet, cm−1): 3420m(υO−H), 3127w, 2965w(υC−H), 2854w(υC−H), 1655s(υasCO), 1514w, 1429m, 1401m, 1384m, 1325w, 1161m(υPO), 1114s(υP−O), 1072m(υP−O), 1050m(υP−O), 1036m(υP−O), 1008w, 933w, 839w, 802m, 777m, 518w. Synthesis of [Zn(HL1)]·CH3COOH (2). A mixture of Zn(CH3COO)2·2H2O (0.0670 g, 0.305 mmol) and H3L1 (0.0943 g, 0.305 mmol) in 6.0 mL of distilled water with the pH value adjusted to 2.18 was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 120 °C for 10 h. After slow cooling to room temperature, colorless prism-like crystals of 2 were obtained as a homogeneous phase based on powder XRD patterns. Yield: 0.0461 g (35%). Anal. Calc. for C16H18NO7PZn: C 44.41, H 4.19, N 3.24%. Found: C 43.62, H 4.22, N 3.24%. IR (KBr pellet, cm−1): 3415m, 3127m, 2954w(υC−H), 2846w(υC−H), 1720s, 1639s(υasCO), 1514w, 1430m, 1402m, 1384m, B



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Table 1. Crystal Data and Refinement Details for Compounds 1−3

a

compounds

1

2

3

formula FW space group a (Å) b (Å) c (Å) β (deg) V (Å3) Z T (K) measured/unique/observed reflections Dcalcd (g cm3) μ (mm−1) GOF on F2 Rint R1a [I > 2σ(I)] wR2b [all data]

C42H48N3O18P3Zn3 1171.85 P2(1)/c 15.836(7) 30.646(15) 9.761(5) 90.144(10) 4737(4) 4 293(2) 34435/10402/8407 1.643 1.686 1.185 0.0951 0.0984 0.2216

C16H18NO7PZn 432.65 C2/c 36.374(8) 10.049(2) 9.784(3) 90.023(14) 3531.9(14) 8 293(2) 10674/3832/2799 1.627 1.520 1.014 0.0550 0.0845 0.2601

C11H12NO7PZn 366.56 P2(1)/c 13.922(6) 10.173(4) 9.772(4) 105.705(6) 1332.4(10) 4 293(2) 14030/3065/2647 1.827 1.997 1.102 0.0478 0.0424 0.0928

R1 = ∑(||Fo| − |Fc||)/∑|Fo|. bwR2 = {∑w[(Fo2 − Fc2)]/∑w[(Fo2)2]}0.5.

Table 2. Crystal Data and Refinement Details for Compounds 4−6

a

compounds

4

5

6

formula FW space group a (Å) b (Å) c (Å) β (deg) V (Å3) Z T (K) measured/unique/observed reflections Dcalcd (g cm3) μ (mm−1) GOF on F2 Rint R1a [I > 2σ(I)] wR2b [all data]

C22H26N2O14P2Mn 659.33 C2/c 32.637(18) 8.417(4) 9.855(6) 106.696(9) 2593(2) 4 293(2) 8655/2837/2267 1.689 0.710 1.085 0.0467 0.0484 0.1040

C22H26N2O14P2Mn 659.33 C2/c 35.591(16) 8.449(4) 9.836(4) 101.970(7) 2894(2) 4 293(2) 15117/3317/2900 1.513 0.636 1.101 0.0344 0.0355 0.0845

C11H14NO8PZn 384.57 P2(1)/c 17.27(2) 8.377(10) 10.153(13) 105.296(19) 1416(3) 4 293(2) 10031/3169/2357 1.803 1.888 1.147 0.0586 0.1291 0.3792

R1 = ∑(||Fo| − |Fc||)/∑|Fo|. bwR2 = {∑w[(Fo2 − Fc2)]/∑w[(Fo2) 2]}0.5.

Table 3. Selected Bond Lengths (Å) and Angles (deg) for 1 Zn(1)−O(1) Zn(1)−O(3)a Zn(1)−O(6) Zn(1)−O(9)b Zn(2)−O(2) Zn(2)−O(7) O(1)−Zn(1)−O(3)a O(1)−Zn(1)−O(6) O(1)−Zn(1)−O(9)b O(3)a-Zn(1)−O(6) O(3)a-Zn(1)−O(9)b O(6)−Zn(1)−O(9)b O(2)−Zn(2)−O(7) O(2)−Zn(2)−O(13)c O(2)−Zn(2)−O(14)d a

Zn(2)−O(13)c Zn(2)−O(14)d Zn(3)−O(4)e Zn(3)−O(8) Zn(3)−O(11) Zn(3)−O(12)d O(7)−Zn(2)−O(13)c O(7)−Zn(2)−O(14)d O(13)c−Zn(2)−O(14)d O(4)e−Zn(3)−O(8) O(4)e−Zn(3)−O(11) O(4)e−Zn(3)−O(12)d O(8)−Zn(3)−O(11) O(8)−Zn(3)−O(12)d O(11)−Zn(3)−O(12)d

1.913(5) 1.940(4) 1.924(4) 1.978(5) 1.926(4) 1.924(5) 101.2(2) 113.2(2) 114.9(2) 115.95(19) 103.3(2) 108.0(2) 112.5(2) 115.94(19) 103.65(19)

1.933(4) 1.972(5) 1.979(5) 1.941(4) 1.918(4) 1.919(4) 102.00(19) 117.8(2) 105.4(2) 103.4(2) 117.3(2) 104.03(18) 100.66(19) 117.10(19) 114.42(19)

Symmetry codes. x, −y + 3/2, z − 1/2. bx, −y + 3/2, z + 1/2. cx, y, z + 1. d-x + 1, −y + 1, −z. ex, y, z − 1.

C



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Table 4. Selected Bond Lengths (Å) and Angles (deg) for 2 Zn(1)−O(1) Zn(1)−O(2)a O(1)−Zn(1)−O(2)a O(1)−Zn(1)−O(3)b O(1)−Zn(1)−O(4)c a

Zn(1)−O(3)b Zn(1)−O(4)c O(2)a−Zn(1)−O(3)b O(2)a−Zn(1)−O(4)c O(3)b−Zn(1)−O(4)c

1.921(4) 1.894(3) 113.86(14) 102.09(13) 116.68(18)

1.922(3) 1.956(4) 113.95(14) 106.64(14) 103.31(16)

Symmetry codes. −x + 1/2, −y + 1/2, −z + 1. bx, −y + 1, z + 1/2. c−x + 1/2, y + 1/2, −z + 1/2.



1.902(2) 1.920(2) 115.39(10) 113.49(10) 106.03(9)

1.929(2) 1.971(2) 102.37(9) 117.06(10) 101.86(10)

Symmetry codes. −x + 2, −y + 1, −z + 1. b−x + 2, y − 1/2, −z + 3/2. cx, −y + 1/2, z − 1/2.

Table 6. Selected Bond Lengths (Å) and Angles (deg) for 4 Mn(1)−O(1) Mn(1)−O(1)a Mn(1)−O(2)b O(1)−Mn(1)−O(1)a O(1)−Mn(1)−O(2)b O(1)−Mn(1)−O(2)c O(1)−Mn(1)−O(4)d O(1)−Mn(1)−O(4)e O(1)a−Mn(1)−O(2)b O(1)a−Mn(1)−O(2)c O(1)a−Mn(1)−O(4)d a

Mn(1)−O(2)c Mn(1)−O(4)d Mn(1)−O(4)e O(1)a−Mn(1)−O(4)e O(2)b−Mn(1)−O(2)c O(2)b−Mn(1)−O(4)d O(2)b−Mn(1)−O(4)e O(2)c−Mn(1)−O(4)d O(2)c−Mn(1)−O(4)e O(4)d−Mn(1)−O(4)e

2.0854(19) 2.0854(19) 2.177(2) 180.0 93.62(8) 86.38(8) 92.64(8) 87.36(8) 86.38(8) 93.62(8) 87.36(8)

2.177(2) 2.244(2) 2.244(2) 92.64(8) 180.00(10) 89.74(8) 90.26(8) 90.26(8) 89.74(8) 180.00(10)

Symmetry codes. −x + 1/2, −y + 3/2, −z. bx, −y + 2, z − 1/2. c−x + 1/2, y − 1/2, −z + 1/2. d−x + 1/2, y + 1/2, −z + 1/2. ex, −y + 1, z − 1/2.

Table 7. Selected Bond Lengths (Å) and Angles (deg) for 5 Mn(1)−O(1) Mn(1)−O(1)a Mn(1)−O(2)b O(1)−Mn(1)−O(1)a O(1)−Mn(1)−O(2)b O(1)−Mn(1)−O(2)c O(1)−Mn(1)−O(4)d O(1)−Mn(1)−O(4)e O(1)a−Mn(1)−O(2)b O(1)a−Mn(1)−O(2)c O(1)a−Mn(1)−O(4)d a

Mn(1)−O(2)c Mn(1)−O(4)d Mn(1)−O(4)e O(1)a−Mn(1)−O(4)e O(2)b−Mn(1)−O(2)c O(2)b−Mn(1)−O(4)d O(2)b−Mn(1)−O(4)e O(2)c−Mn(1)−O(4)d O(2)c−Mn(1)−O(4)e O(4)d−Mn(1)−O(4)e

2.0862(13) 2.0862(13) 2.1713(14) 180.00(11) 93.26(6) 86.74(6) 92.38(5) 87.62(5) 86.74(6) 93.26(6) 87.62(5)

2.1713(14) 2.2331(16) 2.2331(16) 92.38(5) 180.00(9) 89.59(5) 90.41(5) 90.41(5) 89.59(5) 180.00(9)

Symmetry codes. −x + 1/2, −y + 1/2, −z. bx, −y, z − 1/2. c−x + 1/2, y + 1/2, −z + 1/2. d−x + 1/2, y − 1/2, −z + 1/2. ex, − y + 1, z − 1/2.



1.956(10) 1.947(10) 110.8(5) 110.0(5) 112.0(5)

1.949(11) 2.011(11) 117.8(5) 108.3(5) 97.2(5)

Symmetry codes. x, −y + 1/2, z + 1/2. b−x + 1, y + 1/2, −z − 1/2. cx, y + 1, z. respectively. CCDC 1055630 (1), 1055631 (2), 1031914 (3), 1031915 (4), 1031916 (5), and 1031917 (6).

using graphite-monochromated Mo Kα radiation (λ(Mo−Kα) = 0.71073 Å). Data of 1−6 were reduced with CrystalClear v1.3. Their structures were solved by direct methods and refined by full-matrix least-squares techniques on F2 using SHELXTL-97.16 All nonhydrogen atoms were treated anisotropically. Hydrogen atoms were generated geometrically. Crystallographic data for compounds 1−3 and 4−6 are summarized in Tables 1 and 2, respectively. Selected bond lengths and angles for compounds 1−6 are listed in Tables 3−8,

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RESULTS AND DISCUSSION

Synthesis and Characterization. Compounds 1−6 were synthesized by the reaction of Zn(CH3COO)2·2H2O, Mn(CH3COO)2·4H2O, H3L1, H4L2, and H4L3 under hydroD



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exhibits a tetradentate mode to combine four Zn(II) ions through three phosphonate and one carboxylate oxygen atoms (Figure 1c). The protonated nitrogen atoms provide hydrogen atoms to form hydrogen bondings with lattice water molecules (N1···O16, 2.906(9) Å, N2···O17, 2.851(9) Å, and N3···O18, 2.863(9) Å). On the other hand, each lattice molecule also provides one hydrogen atom to generate one hydrogen bonding with the uncoordinated carboxylate oxygen atom of HL12− anion (O16···O15d, 2.907(8) Å; O17···O10b, 2.925(8) Å, and O18···O 5f, 2.815(9) Å). In the bc plane, each [ZnO4] tetrahedron shares three corners with neighboring three [PCO3] tetrahedra into a Zn−O−P layer, which contains eight and four member rings (MRs) (Figure 2a). The organic

thermal conditions. Powder XRD patterns of compounds 1−6 are in agreement with those of simulated single-crystal X-ray data, respectively. Furthermore, elemental analyses of compounds 1−6 accord with respective calculated values. These results suggest that the final products of compounds 1−6 are in the homogeneous phase. During the synthesis of compound 6, many experiments have been performed under different ratios of Zn(CH3COO)2·2H2O/H4L3 and pH values of the reaction mixture. The results indicate that a pure phase of solid 6 can be obtained with the ratio of Zn(CH3COO)2·2H2O/H4L3 in a range of 0.529−0.653 and the pH value in a narrow range of 2.34−2.39. Structural Descriptions. The asymmetric unit of 1 contains three Zn(II) ions and three HL12− anions, as well as three lattice water molecules (Figure 1a). Zn1 is surrounded by

Figure 1. Ball−stick view of (a, b) the coordinated environment of Zn(II) ions and (c) the coordination modes of HL12− anions in 1. Blue-green lines represent hydrogen bonding. Unrelated atoms are omitted for clarity. Symmetry codes: a x, −y + 3/2, z − 1/2; b x, −y + 3/2, z + 1/2; c x, y, z + 1; d −x + 1, −y + 1, −z; e x, y, z − 1; f −x + 1, −y + 1, −z + 1.

Figure 2. Polyhedral view of (a) Zn−O−P layer, (b) 2D sandwich-like framework, and (c) 3D structure in 1. [ZnO4]: green tetrahedron; [PCO3]: yellow tetrahedron. Unrelated atoms are omitted for clarity.

four HL12− anions into a distorted [ZnO4] tetrahedral coordination geometry (Figure 1b). Three HL12− anions interact with Zn1 through three phosphonate oxygen atoms (O1, O3a, O6), respectively, while the fourth HL12− anion contacts Zn1 via one carboxylate oxygen atom (O9b). The coordination environments of Zn2 and Zn3 atoms are similar to that of Zn1 atom. The bond lengths of Zn−O are in the range of 1.913(5)−1.979(5) Å, which match those of reported zinc phosphonates.14 On the other hand, each HL12− anion

groups of HL12− anions hang on two sides of the Zn−O−P layer to generate a two-dimensional (2D) sandwich-like framework (Figure 2b). And these 2D frameworks are further packed into a 3D structure through van der Waals’ force (Figure 2c). As shown in Figure 3a, the asymmetric unit of 2 includes one Zn(II) ion and one HL12− anion, as well as one acetic acid. Same as that in 1, Zn1 is also surrounded by four HL12− anions in a distorted [ZnO4] tetrahedral coordination geometry. Three E



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provides one hydrogen atom to form one hydrogen bonding with acetic acid (N1···O6, 2.780(8) Å). Second, the protonated oxygen atom (O7) of the acetic acid provides one hydrogen atom to generate one hydrogen bonding with the carboxylate group of HL12− anion (O7···O 5d, 2.649(11) Å). Compound 3 crystallizes in monoclinic space group P2(1)/c. As illustrated in Figure 4a, the asymmetric unit of 3 consists of one Zn(II) ion and one H2L22− anion. Zn1 is surrounded by four oxygen atoms from four equivalent H2L22− anions into a distorted [ZnO4] tetrahedral coordination geometry. Three H2L22− anions interact with Zn1 through three phosphonate oxygen atoms (O1, O2a, O3b), respectively, while the fourth H2L22− anion contacts Zn1 via one carboxylate oxygen atom (O4c). The bond lengths of Zn−O are in the range of 1.902(2)−1.971(2) Å, which match with those of reported zinc phosphonates.14 On the other hand, H2L22− anion exhibits a tetradentate mode to combine four Zn(II) ions through three phosphonate and one carboxylate oxygen atoms. Although the other carboxylate oxygen atom (O5), the benzoate group (O6, O7), as well as the nitrogen atom (N1) do not coordinate with Zn(II) ions, they are involved in the formation of hydrogen bondings as follows. First, the protonated benzoate oxygen atom (O6) provides the hydrogen atom (H2) to form a strong hydrogen bonding with the uncoordinated carboxylate oxygen atom (O 5d): O6···O 5d = 2.575(4) Å. Second, the other benzoate oxygen atom (O7e) hydrogen bonds with the protonated nitrogen atom (N1): N1···O7e = 2.790(4) Å. In the bc plane, each [ZnO4] tetrahedron shares three corners with neighboring three [PCO3] tetrahedra into a Zn−O−P layer, which consists of eight and four MRs (Figure 4b). The benzoate groups are oriented in a zipper-like fashion oblique to the Zn−O−P layer to generate a 2D sandwich-like framework (Figure 4c). These 2D frameworks are further interconnected into 3D structure via the above-mentioned hydrogen bondings (Figure 4d). This is similar to those of metal phosphonates based on 4-HOOCC6H4CH2N (CH2PO3H2)2.15 Compound 4 crystallizes in monoclinic space group C2/c. As shown in Figure 5a, the asymmetric unit of 4 comprises half a Mn(II) ion and one H3L2− anion. Mn1 is surrounded by six oxygen atoms from six equivalent H3L2− anions into a slightly distorted [MnO6] octahedral coordination geometry. On the basal plane of [MnO6] octahedron, four H3L2− anions contact with Mn1 through four phosphonate oxygen atoms, respectively, while two polar sites of [MnO6] octahedron are occupied by two carboxylate oxygen atoms from two different H3L2− anions. The bond lengths of Mn−O are in the range of 2.0854(19)−2.244(2) Å. These values are in agreement with those of reported manganese phosphonates.17 On the other hand, H3L2− anion exhibits a tridentate mode to bridge three Mn(II) ions through two phosphonate and one carboxylate oxygen atoms. This is different from the tetradentate mode of H2L22− anion in 3, while the remaining phosphonate (O3) and carboxylate (O5) oxygen atoms, benzoate group (O6, O7), as well as the nitrogen atom (N1) are involved in the formation of three hydrogen bondings as follows. First, the protonated phosphonate oxygen atom (O3) provides one hydrogen atom (H1) to form a strong hydrogen bonding with the uncoordinated carboxylate oxygen atom (O5f): O3···O5f = 2.545(3) Å. Second, the protonated benzoate oxygen atom (O7) supplies one hydrogen atom (H2) to generate a strong hydrogen bonding with the other benzoate oxygen atom from another H3L2− anion (O6g): O7···O6g = 2.615(4) Å. Finally, the protonated nitrogen atom (N1) provides the hydrogen

Figure 3. (a) Ball−stick view of the coordinated environment of Zn(II) ion, polyhedral view of (b) Zn−O−P layer, and (c) the 3D structure in 2. [ZnO4]: green tetrahedron; [PCO3]: yellow tetrahedron. Blue-green lines represent hydrogen bonding. Unrelated atoms are omitted for clarity. Symmetry codes: a −x + 1/2, −y + 1/2, −z + 1; b x, −y + 1, z + 1/2; c −x + 1/2, y + 1/2, −z + 1/2; d x, −y, z + 1/2.

HL12− anions interact with Zn1 through three phosphonate oxygen atoms (O1, O2a, O3b), respectively, while the fourth HL12− anion contacts Zn1 via one carboxylate oxygen atom (O4c). The bond lengths of Zn−O are in the range of 1.894(3)−1.956(4) Å, which also match those of reported zinc phosphonates.14 Similar to those in 1, the HL12− anion also exhibits a tetradentate mode to combine four Zn(II) ions through three phosphonate and one carboxylate oxygen atoms. Thus, each [ZnO4] tetrahedron shares three corners with neighboring three [PCO3] tetrahedra into a Zn−O−P layer (Figure 3b), which contains eight and four MRs. The organic groups of HL12− anions hang on two sides of the Zn−O−P layer to form a 2D sandwich-like framework. These 2D frameworks are also further packed into a 3D structure through van der Waals’ force (Figure 3c). In addition, the acetic acid is incorporated between layers through two strong hydrogen bondings as follows. First, the protonated nitrogen atom (N1) F



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Figure 4. (a) Ball−stick view of the coordinated environment of Zn(II) ion and the coordination mode of H2L22− anion, polyhedral view of Zn−O−P layer (b), 2D sandwich-like framework (c), and 3D structure (d) in 3. [ZnO4]: green tetrahedron; [PCO3]: yellow tetrahedron. Blue-green lines represent hydrogen bondings. Unrelated atoms are omitted for clarity. Symmetry codes: a −x + 2, −y + 1, −z + 1; b −x + 2, y − 1/2, −z + 3/2; c x, −y + 1/2, z − 1/2; d −x + 1, −y + 1, −z + 2; e −x + 1, y − 1/2, −z + 3/2.

Figure 5. (a) Ball−stick view of the coordinated environment of Mn(II) ion and the coordination mode of H3L2− anion, polyhedral view of Mn−O−P layer (b), 2D sandwich-like framework (c), and 3D structure (d) in 4. [MnO6]: pink octahedron; [PCO3]: yellow tetrahedron. Blue-green lines represent hydrogen bondings. Unrelated atoms are omitted for clarity. Symmetry codes: a −x + 1/2, −y + 3/2, −z; b x, −y + 2, z − 1/2; c −x + 1/2, y − 1/2, −z + 1/2; d −x + 1/2, y + 1/2, −z + 1/2; e x, −y + 1, z − 1/2; f x, y + 1, z; g −x + 1, −y + 1, −z + 2.

atom (H3) to form a hydrogen bonding with one phosphonate oxygen atom (O2c): N1···O2c = 2.869(3) Å. Each [MnO6] octahedron shares four corners with neighboring four [PCO3] tetrahedrons, resulting in a Mn−O−P layer. The Mn−O−P layer consists of eight MRs (Figure 5b). Similar to those in compound 3, the benzoate groups are also oriented in a zipper-

like fashion oblique to these Mn−O−P layers, resulting in a 2D sandwich-like framework (Figure 5c). These 2D frameworks are further held together into a 3D structure by hydrogen bondings between benzoate groups (Figure 5d). G



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Compound 5 is also structurally characterized (Figure S7, Supporting Information). The chemical composition and structure of 5 is similar to those of 4 except that H3L2− anion in 4 is replaced by H3L3− anion. The main difference between structures of 4 and 5 is the unit cell volume. In compound 5, the unit cell volume is 2894(2) Å3, which is larger than that in 4 (2593(2) Å3). Similar to that of compound 3, compound 6 also crystallizes in monoclinic space group P2(1)/c. As shown in Figure 6a, the asymmetric unit of 6 contains one Zn(II) ion, one H2L32− anion, and one lattice water molecule. Zn1 is in a distorted [ZnO4] tetrahedral coordination geometry, which is defined by four oxygen atoms from four equivalent H2L32− anions. Three H2L32− anions are interacted with Zn1 through three phosphonate oxygen atoms (O1, O2a, O3b), respectively, while the fourth H2L32− anion contacts Zn1 via one carboxylate oxygen atom (O4c). The bond lengths of Zn−O are in the range of 1.947(10)−2.011(11) Å, which are in agreement with those of reported zinc phosphonates.14 On the other hand, H2L32− anion exhibits a tetradentate mode to combine four Zn(II) ions through three phosphonate and one carboxylate oxygen atoms. In the bc plane, each [ZnO4] tetrahedron shares three corners with neighboring three [PCO3] tetrahedra into a Zn−O−P layer. Same to those in compounds 1 and 3, the Zn− O−P layer also consists of eight and four MRs (Figure 6b). The benzoate groups are oriented perpendicular to two sides of Zn−O−P layer to form a 2D sandwich-like framework (Figure 6c). As shown in Figure 6d, these 2D frameworks are held together by strong hydrogen bondings between the protonated benzoate group and carboxylate oxygen atom (O6···O 5d, 2.676(16) Å), resulting in the formation of a 3D structure. In addition, the lattice water molecule contacts the hybrid layer through hydrogen bonding (N1···O8, 2.889(18) Å). Comparing compounds 1−6 and those of reported metal phosphonates, it seems that the additional groups have an obvious impact on their structures. Except for N(CH2COOH)(CH2PO3H2) moiety, there is no additional group of H3L1 in compounds 1−2. Thus, the 2D framework of compounds 1−2 cannot be further extended into a 3D framework. Although the benzoate groups of H4L2 and H4L3 in compounds 3−6 are protonated and do not take part in coordination with metal ions, they can bridge the 2D frameworks of compounds 3−6 into a 3D structure by hydrogen bondings. In contrast, [Zn3(L)2]·2H2O and (H3O)4[Cd7(L)6]·16H2O (H3L = 4pyridyl-CH2N(CH2COOH)(CH2PO3H2)) exhibit 3D frameworks because the deprotonated pyridyl also bonds to metal ions.14a,c Thermal Stabilities. TGA and powder XRD measurements were carried out to examine thermal stabilities (Figure 7). For solid 1, a slight stage occurs from room temperature to 220 °C with a 4.77% weight loss, which is attributed to the loss of three lattice water molecules (calculated 4.61%). Upon further heating, an abrupt stage appears due to the decomposition of the HL12− anion. As a result, the 2D framework collapses. A TGA curve of 2 illustrates that there is a slight stage in the temperature range of 38−230 °C, which is attributed to the loss of the acetic acid. Then, the subsequent weight loss over 230 °C is assigned to the decomposition of HL12− anion and the collapse of the 2D framework. For 1, the overall weight loss of 62.3% is close to the calculated value (61.1%) assuming that the residue is Zn2P2O7,15d while for 2, the total weight loss of 70.4% is in agreement with the calculated value (70.2%) assuming that the residue is a mixture of ZnO and Zn2P2O7 in a

Figure 6. (a) Ball−stick view of the coordinated environment of Zn(II) ion and the coordination mode of H2L32− anion, polyhedral view of Zn−O−P layer (b), 2D sandwich-like framework (c), and 3D structure (d) in 6. [ZnO4]: green tetrahedron; [PCO3]: yellow tetrahedron. Blue-green lines represent hydrogen bondings. Unrelated atoms are omitted for clarity. Symmetry codes: a x, − y + 1/2, z + 1/2; b −x + 1, y + 1/2, −z − 1/2; c x, y + 1, z; d −x + 2, y + 1/2, −z + 1/2.

molar ratio of 1:1. TGA curves of solids 3, 4, and 5 illustrate that there are little weight losses up to 330, 300, and 250 °C, respectively. Upon further heating, abrupt weight loss stages appear corresponding to the decomposition of H2L22−, H3L2−, and H3L3− anions for solids 3, 4, and 5, respectively. As a result, the sandwich-like 2D frameworks of solids 3−5 collapse. H



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Figure 7. TGA curves of solids 1−6.

Figure 8. Emission spectra for solids 1−2.

For 3, the overall weight loss of 78.7% matches the calculated value (77.8%) assuming that the residue is ZnO. The overall weight losses for solids 4 and 5 are 70.5% and 73.8%, respectively. TGA curve of 6 illustrates that there is a stage in the temperature range of 38−250 °C with a 5.36% weight loss, which is attributed to the loss of one lattice water molecules (calculated 4.68%). Upon further heating, an abrupt stage starts from 300 °C due to the decomposition of H2L32− anion, resulting in the collapse of the 2D framework. For 6, the total weight loss of 67.7% is close to the calculated value (66.5%) assuming that the residue is a mixture of ZnO and Zn2P2O7 in a molar ratio of 1:1. Powder XRD patterns of solids 2-180, 3-250, 4-230, and 6250 are in agreement with those of as-prepared 2, 3, 4, and 6, respectively. These results illustrate that the 2D frameworks of compounds 2, 3, 4, and 6 are thermally stable up to 180, 250, 230, and 250 °C under an air atmosphere, respectively. The different thermal stabilities of these solids might be attributed to the different phosphonate ligands. On the other hand, unit cell parameters of solid 3-250 are a = 13.84, b = 10.12, c = 9.70 Å, α = 90, β = 105.75, γ = 90, V = 1308 Å3, which are similar to those of pristine 3. This is in accord with thermal stability of compound 3. Furthermore, after solid 6-250 was soaked in water for 3 days, powder XRD patterns are also in agreement with those of pristine 6. This indicates that the 2D framework of 6 is a good resistance to water that could be ascribed to chemical stability of metal phosphonates.18 Luminescent Properties. Solid-state luminescent properties were investigated under ambient temperature. The H3L1 can give off weak UV emission with a maximum band at 344 nm upon excitation at 277 nm, while no emission for H4L2 and H4L3 can be detected under our experiment. In contrast, solids 1−2 display bright UV luminescence with maximum bands at 363 and 343 nm (Figure 8), respectively. Since the excitation profiles of 1−2 are similar to those of H3L1, the bright UV emission of solids 1−2 may be assigned to ligand-centered π−π* transition. The emission peak of 1 shows a 19 nm bathochromic shift in comparison with that of H3L1. In addition, the bright UV luminescence of solid 2 can be preserved after compound 2 was heated at 180 °C for 2 h under an air atmosphere. This accords with the observation that the 2D framework of solid 2 is thermally stable up to 180 °C under an air atmosphere. Furthermore, it is interesting that luminescent intensities of solids 1, 2, and 2-180 can be irreversibly quenched by UV irradiation (Figures 9−10 and S12). For example, after irradiation with UV radiation at 272

Figure 9. Emission spectra for compound 1 with different UV irradiation times at 272 nm. Inset: emission intensity at λmax(em) as a function of UV irradiation time at 272 nm.

Figure 10. Emission spectra for compound 2 with different UV irradiation times at 270 nm. Inset: emission intensity at λmax(em) as a function of UV irradiation time at 270 nm.

nm (for 1) and 270 nm (for 2) for 10 min, luminescent intensity of compounds 1−2 can be weakened about 50%. And after solids 1 and 2 were irradiated with a UV lamp at 254 nm for 48 h, powder XRD patterns are in agreement with those of as-prepared 1−2, respectively. This result indicates the quenching mechanism excludes the changes in their 2D frameworks. The concomitant suppression of emission under I



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functionalized phosphonic acids by the combination of the N(CH2COOH)(CH2PO3H2) moiety with fluorophores, such as quinoline and anthracene. Then, such functionalized phosphonate ligands will be exploited to prepare new luminescent metal phosphonates with interesting structures.

UV irradiation is similar to those of previously reported zinc phosphonates.14d,e It is well-known that excessive exposure to UV radiation would cause skin cancer, cataracts, and other eye diseases. And the eyes are most sensitive to UV radiation, particularly the wavelength around 280 nm. Furthermore, UV radiation is invisible and therefore does not stimulate the natural defenses of the eyes. Thus, a simple component, facile synthesis and high thermal stability make solid 2 an attractive material to be used for the sensing of UV radiation. Both solids 3−4 can emit weak blue-green light upon excitation around 365 nm. The lifetimes of λem = 445 nm (for 3) and λem = 484 nm (for 4) are 5.7(2) and 7.2(4) ns, respectively. Solid 6 displays blue luminescence with a maximum band at 447 nm upon excitation at 327 nm (Figure 11). The lifetime of λem = 445 nm is 3.5(2) ns. Similar to those

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ASSOCIATED CONTENT

S Supporting Information *

Crystallographic data in CIF format (CCDC 1055630 (1), 1055631 (2), 1031914 (3), 1031915 (4), 1031916 (5), and 1031917 (6)), PXRD patterns, additional structural figures and luminescent plots. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/ acs.cgd.5b00423.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel: +86-591-63173277. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This research was supported by grants from the National Science Foundation of China (21173220 and 21373219) and the National Basic Research Program of China (973 Program, 2012CB821702).

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REFERENCES

(1) (a) Gagnon, K. J.; Perry, H. P.; Clearfield, A. Chem. Rev. 2012, 112, 1034−1054. (b) Clearfield, A.; Demadis, K. Metal Phosphonate Chemistry From Synthesis to Applications; The Royal Society of Chemistry: Cambridge, U.K., 2012. (c) Boldog, I.; Domasevitch, K. V.; Baburin, I. A.; Ott, H.; Gil-Hernández, B.; Sanchiz, J.; Janiak, C. CrystEngComm 2013, 15, 1235−1243. (d) Tang, S. F.; Li, L. J.; Wang, C.; Zhao, X. B. CrystEngComm 2014, 16, 9104−9115. (e) Tang, S. F.; Li, L. J.; Lv, X. X.; Wang, C.; Zhao, X. B. CrystEngComm 2014, 16, 7043−7052. (2) (a) Gagnon, K. J.; Beavers, C. M.; Clearfield, A. J. Am. Chem. Soc. 2013, 135, 1252−1258. (b) Liang, X. Q.; Zhang, F.; Feng, W.; Zou, X. Q.; Zhao, C. J.; Na, H.; Liu, C.; Sun, F. X.; Zhu, G. S. Chem. Sci. 2013, 4, 983−992. (c) Zheng, Y. Z.; Evangelisti, M.; Tuna, F.; Winpenny, R. E. P. J. Am. Chem. Soc. 2012, 134, 1057−1065. (d) Bao, S. S.; Otsubo, K.; Taylor, J. M.; Jiang, Z.; Zheng, L. M.; Kitagawa, H. J. Am. Chem. Soc. 2014, 136, 9292. (e) Tang, S. F.; Cai, J. J.; Li, L. J.; Lv, X. X.; Wang, C.; Zhao, X. B. Dalton Trans. 2014, 43, 5970−5973. (3) (a) Zhang, L.; Clérac, R.; Heijboer, P.; Schmitt, W. Angew. Chem., Int. Ed. 2012, 51, 3007−3011. (b) Zheng, Y. Z.; Pineda, E. M.; Helliwell, M.; Winpenny, R. E. P. Chem.Eur. J. 2012, 18, 4161− 4165. (c) Zheng, Y. Z.; Evangelisti, M.; Winpenny, R. E. P. Chem. Sci. 2011, 2, 99−102. (d) Xie, Y. P.; Mak, T. C. W. Dalton Trans. 2013, 42, 12869−12872. (e) Wang, T. T.; Ren, M.; Bao, S. S.; Liu, B.; Pi, L.; Cai, Z. S.; Zheng, Z. H.; Xu, Z. L.; Zheng, L. M. Inorg. Chem. 2014, 53, 3117−3125. (4) (a) Colodrero, R. M. P.; Papadaki, M.; Garczarek, P.; Zoń, J.; Olivera-Pastor, P.; Losilla, E. R.; León-Reina, L.; Aranda, M. A. G.; Choquesillo-Lazarte, D.; Demadis, K. D.; Cabeza, A. J. Am. Chem. Soc. 2014, 136, 5731−5739. (b) Ren, M.; Bao, S. S.; Ferreira, R. A. S.; Zheng, L. M.; Carlos, L. D. Chem. Commun. 2014, 50, 7621−7624. (c) Yang, X. J.; Bao, S. S.; Ren, M.; Hoshino, N.; Akutagawa, T.; Zheng, L. M. Chem. Commun. 2014, 50, 3979−3981. (5) (a) Taddei, M.; Costantino, F.; Ienco, A.; Comotti, A.; Daud, P. V.; Cohend, S. M. Chem. Commun. 2013, 49, 1315−1317. (b) Yang, X. J.; Bao, S. S.; Zheng, T.; Zheng, L. M. Chem. Commun. 2012, 48, 6565−6567. (c) Begum, S.; Wang, Z. Y.; Donnadio, A.; Costantino, F.; Casciola, M.; Valiullin, R.; Chmelik, C.; Bertmer, M.; Kärger, J.; Haase, J.; Krautscheid, H. Chem.Eur. J. 2014, 20, 8862−8868.

Figure 11. Emission spectra for solids 6 and 6-250.

of solids 1−2, the blue emission of solid 6 can also be irreversibly quenched by UV irradiation (Figure S18). After heating treatment at 250 °C, solid 6-250 can emit blue-green emission with a maximum band at 491 nm upon excitation at 372 nm. The emission profile is very broad. The fwhm is 137 nm, which exhibits a 47 nm broader than that of pristine 6. In addition, it is interesting that the maximum band of solid 6-250 shows a 44 nm red-shift compared to that of as-prepared 6. As a result, the emission color was transformed from blue into bluegreen. It worth noting that the blue-green emission can be preserved after solid 6-250 was soaked in water for 3 days. This coincides with observation that the 2D framework of compound 6 has good resistance to water.

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CONCLUSION In summary, we have described the syntheses, crystal structures, thermal stability, and luminescent properties of six new layered metal phosphonates, namely, [Zn3(HL1)3]·3H2O (1), [Zn(HL1)]·CH3COOH (2), [Zn(H2L2)] (3), [Mn(H3L2)2] (4), [Mn(H3L3)2] (5), and [Zn(H2L3)]·H2O (6). Compounds 1− 6 feature 2D sandwich-like frameworks with Zn−O−P (for 1− 3, 6) and Mn−O−P (for 4−5) layers. TGA and powder XRD reveal that 2D frameworks of compounds 2, 3, 4, and 6 are thermally stable up to 180, 250, 230, and 250 °C under an air atmosphere, respectively. It worth noting that both solids 1−2 display bright UV luminescence, which can be irreversibly quenched by UV irradiation. And the blue luminescence of solid 6 can be transformed into blue-green emission by simple heating treatment. In future, we will try to synthesize new J



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